CN114572973B - Method for preparing graphene composite aerogel by intercalation-in-situ polymerization synergistic method - Google Patents
Method for preparing graphene composite aerogel by intercalation-in-situ polymerization synergistic method Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 239000004964 aerogel Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 10
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 10
- 239000000017 hydrogel Substances 0.000 claims abstract description 38
- 238000010008 shearing Methods 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 239000002195 soluble material Substances 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 229910000385 transition metal sulfate Inorganic materials 0.000 claims description 3
- 241000080590 Niso Species 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000004966 Carbon aerogel Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004967 Metal oxide aerogel Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
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Abstract
A method for preparing graphene composite aerogel by an intercalation-in-situ polymerization synergistic method comprises the following steps: (1) preparing sulfate solution with a certain concentration; (2) preparing a polymer water-soluble solution with a certain concentration; (3) preparing sodium stearate solution with a certain concentration; (4) assembling an electrochemical stripping device; (5) preparing graphene composite hydrogel by electrochemical stripping; (6) high-speed shearing and stripping the graphene composite hydrogel; (7) preparing graphene composite aerogel by using an ice template method; (8) And preparing graphene or graphene composite aerogel by a soft template method. The method has the advantages of simple production process, mild conditions, easily obtained raw materials, low cost, relatively green and environment-friendly reaction process and the like, provides a new design concept for preparing the high-performance graphene composite aerogel, and provides a new idea for preparing materials such as macro-scale carbon aerogel in large scale in the future.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a method for preparing graphene composite aerogel by an intercalation-in-situ polymerization synergistic method.
Background
The synthesis of the graphene composite aerogel not only inherits the ultrahigh conductivity and good mechanical properties of graphene, but also has the structural advantages of high specific surface area, low density and the like, and greatly expands the application field of the graphene composite aerogel.
At present, the preparation of graphene composite aerogel is mostly completed by adopting a two-step method, wherein the first step is to prepare graphene dispersion liquid by a Hummers method, and the second step is to synthesize graphene composite aerogel by a hydrothermal method. Therefore, development of a new method for preparing composite aerogel with simple process, mild condition and high speed is urgently needed to realize wider application of graphene composite aerogel.
Based on the problems, the invention provides a novel method for synthesizing graphene composite aerogel in situ. According to the method, transition sulfate is used as an electrolyte, graphite is used as an electrode, and under the action of a direct current power supply, the high-quality graphene composite aerogel with uniform intercalation, fewer defects and thinner layer number can be obtained.
Disclosure of Invention
A graphene or graphene composite aerogel is prepared by the following method:
(1) Preparing a sulfate solution with a certain concentration: weighing a certain amount of metal sulfate or transition metal sulfate, dissolving the metal sulfate or transition metal sulfate in deionized water, and continuously stirring to prepare a solution with the concentration of 0.1 mol/L-5 mol/L;
(2) Preparing a high molecular water-soluble solution with a certain concentration: weighing a certain amount of polymer water-soluble material, adding the polymer water-soluble material into a certain amount of deionized water, heating, stirring and dissolving to prepare a solution with the concentration of 0.1% -10%;
(3) Preparing a sodium stearate solution with a certain concentration: weighing a certain amount of sodium stearate solid, adding the sodium stearate solid into a certain amount of deionized water, heating, stirring and dissolving to prepare a solution with the concentration of 0.1% -10%;
(4) Assembling an electrochemical stripping device: adopting an integrated organic glass plate to self-control an electrolytic tank, wherein an anode and a cathode are both graphite, the two electrodes are respectively connected with the anode and the cathode of a direct current power supply through wires, and simultaneously, the electrolytic tank is placed in a constant-temperature water bath ultrasonic cleaner;
(5) Electrochemical stripping to prepare graphene composite hydrogel: uniformly mixing the components (1) and (2), (1) and (3) according to a certain proportion, and adding the mixture into an electrolytic tank to serve as electrolyte. Under the action of a direct current power supply, electrochemical stripping is carried out by controlling voltage or current, so as to obtain graphene composite hydrogel dispersed in an electrolyte;
(6) High-speed shearing and stripping graphene composite hydrogel: taking out the graphene composite hydrogel in the step (5), pouring the graphene composite hydrogel into a beaker, and further stripping under the action of a high-speed dispersion shearing machine to obtain the graphene composite hydrogel with thinner layers and uniform dispersion;
(7) Preparing graphene composite aerogel by an ice template method: placing the graphene composite hydrogel prepared by high-speed shearing and stripping in the step (6) into a grinding tool, and obtaining the graphene composite aerogel by a freeze drying technology through an ice template method;
(8) And (3) placing the graphene composite aerogel obtained in the step (7) in a tube furnace, and removing the template through high-temperature calcination under the protection of Ar to obtain the graphene or the graphene composite aerogel.
Preferably, the metal sulfate in step (1) is (NH) 4 ) 2 SO 4 、MgSO 4 、Al 2 SO 4 Etc., transition sulfate is Fe 2 (SO 4 ) 3 、CoSO 4 、NiSO 4 、MnSO 4 Etc.
Preferably, the graphite in the step (4) is high-orientation pyrolytic graphite, graphite foil, crystalline flake graphite, expandable graphite or porous graphite electrode, the temperature of the constant-temperature water bath is 30-80 ℃, the power of the ultrasonic cleaner is 100-1000W, and the ultrasonic time is determined according to the electrolysis time.
Preferably, in the step (5), the polymer water-soluble material is polyvinyl alcohol, sodium carboxymethyl cellulose and the like, wherein the ratio of the polymer water-soluble material to sulfate is 0.001-1, the ratio of sodium stearate to sulfate is 0.001-1, and the electrolysis current is 0.1-5A.
Preferably, the rotating speed of the high-speed dispersion shearing machine in the step (6) is 500-6000 r/min, and the shearing and stripping time is 10-60 min.
Preferably, the step (7) adopts a temperature programming mode for freeze drying, wherein the temperature programming rate is 1-10 ℃/h, the drying temperature is-60-100 ℃, and the drying time is 5-30 h.
Preferably, the calcination temperature in the step (8) is 200-1200 ℃, the calcination is 1-h, and the heat preservation is 2-h.
Drawings
FIG. 1 is a graphical representation of graphene aerogel prepared in accordance with the present invention;
fig. 2 is an SEM image of graphene aerogel prepared according to the present invention.
The beneficial effects of the invention are that
According to the preparation method, the graphene composite hydrogel is prepared by adopting an intercalation-in-situ polymerization synergistic method, and the graphene composite aerogel is synthesized by an ice template method and a soft template method. The method takes sulfate as electrolyte, and a small amount of high molecular water-soluble material or sodium stearate is added to prepare the composite aerogel by a one-step method. The graphene aerogel in the produced product has good mechanical property and electrical property, and can be used in the fields of super capacitors, batteries and the like; the graphene/metal oxide aerogel can be used as an energy storage material, an electromagnetic shielding material and the like. Compared with the traditional process, the method has the advantages of simple production process, mild condition, easily available raw materials, low cost, relatively green and environment-friendly reaction process and the like, provides a new design concept for preparing the high-performance graphene composite aerogel, and provides a new idea for preparing materials such as macro-scale carbon aerogel in large quantity in the future.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention. The technical proposal of the invention can realize the products required by the invention by the values of the technological parameters on the upper line and the lower line and the intervals.
Example 1
(1) Preparing ammonium sulfate solution with a certain concentration: weighing a certain amount of anhydrous ammonium sulfate, dissolving the anhydrous ammonium sulfate in deionized water, and continuously stirring to prepare a solution with the concentration of 0.8 mol/L;
(2) Preparing a polyvinyl alcohol solution with a certain concentration: weighing a certain amount of polyvinyl alcohol, adding the polyvinyl alcohol into a certain amount of deionized water, heating, stirring and dissolving to prepare a solution with the concentration of 0.5%;
(3) Assembling an electrochemical stripping device: adopting an organic glass plate to self-prepare an electrolytic tank, wherein an anode and a cathode are both high-orientation pyrolytic graphite, the two electrodes are respectively connected with the anode and the cathode of a direct-current power supply through wires, and simultaneously, placing the electrolytic tank in a constant-temperature water bath ultrasonic cleaner, wherein the temperature is 50 ℃, and the power is set to be 500W;
(4) Electrochemical stripping to prepare graphene composite hydrogel: and (3) uniformly mixing the solutions (1) and (2) according to the proportion of 1:0.1, and adding the mixture into an electrolytic tank to serve as electrolyte. Under the action of a direct current power supply, electrochemical stripping is carried out by controlling the current to be 0.5 and A to obtain graphene composite hydrogel dispersed in an electrolyte, wherein the electrochemical stripping is 6 h;
(5) High-speed shearing and stripping graphene composite hydrogel: taking out the graphene composite hydrogel in the step (4), pouring the graphene composite hydrogel into a 1000 mL beaker, shearing for 30 min under the condition that the rotating speed of a high-speed dispersion shearing machine is 2000 r/min, and further stripping to obtain the graphene composite hydrogel with thinner layers and uniform dispersion;
(6) Placing the graphene composite hydrogel prepared by high-speed shearing and stripping in the step (5) into a grinding tool, firstly freezing 2h at the temperature of-40 ℃, and then performing freeze drying in a temperature programming mode, wherein the temperature rising rate is 3 ℃/h, the drying temperature is-40-26 ℃, and the drying time is 24h, so that the graphene composite aerogel is finally obtained;
(7) And (3) placing the graphene composite aerogel obtained in the step (6) in a tube furnace, roasting 1h at 600 ℃ under the protection of Ar, preserving heat 2h, and calcining to remove polyvinyl alcohol to obtain the graphene aerogel.
Example 2
(1) Preparing ferric sulfate solution with a certain concentration: weighing a certain amount of ferric sulfate, dissolving in deionized water, and continuously stirring to prepare a solution with the concentration of 2 mol/L;
(2) Preparing a polyvinyl alcohol solution with a certain concentration: weighing a certain amount of polyvinyl alcohol, adding the polyvinyl alcohol into a certain amount of deionized water, heating, stirring and dissolving to prepare a solution with the concentration of 1%;
(3) Assembling an electrochemical stripping device: adopting an organic glass plate to self-prepare an electrolytic tank, wherein an anode and a cathode are both high-orientation pyrolytic graphite, the two electrodes are respectively connected with the anode and the cathode of a direct-current power supply through wires, and simultaneously, placing the electrolytic tank in a constant-temperature water bath ultrasonic cleaner, wherein the temperature is 70 ℃, and the power is set to 600W;
(4) Electrochemical stripping to prepare graphene composite hydrogel: and (3) uniformly mixing the solutions (1) and (2) according to the proportion of 1:0.1, and adding the mixture into an electrolytic tank to serve as electrolyte. Under the action of a direct current power supply, electrochemical stripping is carried out by controlling the current to be 1A, and 5h of graphene composite hydrogel dispersed in an electrolyte is obtained;
(5) High-speed shearing and stripping graphene composite hydrogel: taking out the graphene composite hydrogel in the step (4), pouring the graphene composite hydrogel into a 1000 mL beaker, shearing for 60min under the condition that the rotating speed of a high-speed dispersion shearing machine is 2000 r/min, and further stripping to obtain the graphene composite hydrogel with thinner layers and uniform dispersion;
(6) Placing the graphene composite hydrogel prepared by high-speed shearing and stripping in the step (5) into a grinding tool, firstly freezing 2h at the temperature of-40 ℃, and then performing freeze drying in a temperature programming mode, wherein the temperature rising rate is 10 ℃/h, the drying temperature is-40-26 ℃, and the drying time is 12 h, so that the graphene composite aerogel is finally obtained;
(7) And (3) placing the graphene composite aerogel obtained in the step (6) in a tube furnace, roasting 1h at 800 ℃ under the protection of Ar, preserving heat 2h, and calcining to remove polyvinyl alcohol to obtain the magnetic graphene aerogel.
Example 3
(1) Preparing a magnesium sulfate solution with a certain concentration: weighing a certain amount of anhydrous magnesium sulfate, dissolving the anhydrous magnesium sulfate in deionized water, and continuously stirring to prepare a solution with the concentration of 0.5 mol/L;
(2) Preparing a sodium carboxymethyl cellulose solution with a certain concentration: weighing a certain amount of sodium carboxymethyl cellulose, adding into a certain amount of deionized water, heating, stirring and dissolving to prepare a solution with the concentration of 0.5%;
(3) Assembling an electrochemical stripping device: adopting an organic glass plate to self-prepare an electrolytic tank, wherein an anode and a cathode are both high-orientation pyrolytic graphite, the two electrodes are respectively connected with the anode and the cathode of a direct-current power supply through wires, and simultaneously, placing the electrolytic tank in a constant-temperature water bath ultrasonic cleaner, wherein the temperature is 40 ℃, and the power is set to be 700W;
(4) Electrochemical stripping to prepare graphene composite hydrogel: and (3) uniformly mixing the solutions (1) and (2) according to the proportion of 1:0.1, and adding the mixture into an electrolytic tank to serve as electrolyte. Under the action of a direct current power supply, electrochemical stripping is carried out by controlling the current to be 2A, so as to obtain graphene composite hydrogel dispersed in an electrolyte, wherein the electrochemical stripping is 3 h;
(5) High-speed shearing and stripping graphene composite hydrogel: taking out the graphene composite hydrogel in the step (4), pouring the graphene composite hydrogel into a 1000 mL beaker, shearing for 60min under the condition that the rotating speed of a high-speed dispersion shearing machine is 5000 r/min, and further stripping to obtain the graphene composite hydrogel with thinner layers and uniform dispersion;
(6) Placing the graphene composite hydrogel prepared by high-speed shearing and stripping in the step (5) into a grinding tool, firstly freezing 2h at the temperature of-40 ℃, and then performing freeze drying in a temperature programming mode, wherein the temperature rising rate is 5 ℃/h, the drying temperature is-40-80 ℃, and the drying time is 30h, so that the graphene composite aerogel is finally obtained;
(7) And (3) placing the graphene composite aerogel obtained in the step (6) in a tube furnace, roasting 1h at 1100 ℃ under the protection of Ar, preserving heat for 4h, and calcining to remove sodium carboxymethyl cellulose to obtain the graphene/magnesium oxide composite aerogel.
The applicant states that the above embodiments are only for illustrating the technical solution of the present invention, and are not intended to limit the scope of the present invention. It will be appreciated by those skilled in the art that any modifications, equivalent substitutions of raw materials, improvements in process, etc. are intended to be within the scope of the present invention.
Claims (6)
1. The method for preparing the graphene composite aerogel by the intercalation-in-situ polymerization synergistic method is characterized by comprising the following steps of:
(1) Preparing a sulfate solution with a certain concentration: weighing a certain amount of metal sulfate or transition metal sulfate, dissolving in deionized water, continuously stirring to prepare a solution with the concentration of 0.1 mol/L-5 mol/L, wherein the metal sulfate is ZnSO 4 、MgSO 4 、Al 2 (SO 4 ) 3 The transition sulfate is Fe 2 (SO 4 ) 3 、CoSO 4 、NiSO 4 、MnSO 4 ；
(2) Preparing a high molecular water-soluble solution with a certain concentration: weighing a certain amount of polymer water-soluble material, adding the polymer water-soluble material into a certain amount of deionized water, heating, stirring and dissolving to prepare a solution with the concentration of 0.1-10%;
(3) Assembling an electrochemical stripping device: adopting an integrated organic glass plate to self-control an electrolytic tank, wherein an anode and a cathode are both graphite, the two electrodes are respectively connected with the anode and the cathode of a direct current power supply through wires, and simultaneously, the electrolytic tank is placed in a constant-temperature water bath ultrasonic cleaner;
(4) Electrochemical stripping to prepare graphene composite hydrogel: uniformly mixing the components (1) and (2) according to a certain proportion, adding the mixture into an electrolytic tank to serve as electrolyte, and carrying out electrochemical stripping under the action of a direct current power supply by controlling voltage or current to obtain graphene composite hydrogel dispersed in the electrolyte, wherein the high-molecular water-soluble material is sodium carboxymethyl cellulose and polyvinyl alcohol; the ratio of the polymer water-soluble material to the sulfate is 0.001-1;
(5) High-speed shearing and stripping graphene composite hydrogel: taking out the graphene composite hydrogel in the step (4), pouring the graphene composite hydrogel into a beaker, and further stripping under the action of a high-speed dispersion shearing machine to obtain the graphene composite hydrogel with thinner layers and uniform dispersion;
(6) Preparing graphene composite aerogel by an ice template method: placing the graphene composite hydrogel prepared by high-speed shearing and stripping in the step (5) into a grinding tool, and obtaining the graphene composite aerogel by a freeze drying technology through an ice template method;
(7) And (3) placing the graphene composite aerogel obtained in the step (6) in a tube furnace, and removing the template through high-temperature calcination under the protection of Ar to obtain the graphene or the graphene composite aerogel.
2. The method for preparing graphene composite aerogel according to claim 1, wherein in the step (3), the graphite is highly oriented pyrolytic graphite, graphite foil, flake graphite, expandable graphite, or porous graphite electrode.
3. The method for preparing the graphene composite aerogel by the intercalation-in-situ polymerization synergistic method according to claim 1, wherein in the step (4), the constant-temperature water bath temperature is 30-80 ℃, the power of an ultrasonic cleaner is 100-1000W, and the ultrasonic time is determined according to the electrolysis time.
4. The method for preparing the graphene composite aerogel by the intercalation-in-situ polymerization synergistic method according to claim 1, which is characterized in that in the step (5), the rotating speed of a high-speed dispersion shearing machine is 500-6000 r/min, and the shearing and stripping time is 10-60 min.
5. The method for preparing the graphene composite aerogel by the intercalation-in-situ polymerization synergistic method according to claim 1, which is characterized in that in the step (6), freeze drying is performed by adopting a temperature programming mode, wherein the temperature raising rate is 1-10 ℃/h, the drying temperature is-60-100 ℃, and the drying time is 5-24 h.
6. The method for preparing the graphene composite aerogel by the intercalation-in-situ polymerization synergistic method according to claim 1, which is characterized in that in the step (7), the calcination temperature is 200-1200 ℃, the calcination is carried out for 1h, and the heat preservation is carried out for 2h.
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