CN108069419B - Macroscopic graphene aerogel and preparation method thereof - Google Patents
Macroscopic graphene aerogel and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 84
- 239000004964 aerogel Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 54
- 239000010439 graphite Substances 0.000 claims abstract description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 150000002978 peroxides Chemical class 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
A preparation method of a macroscopic graphene aerogel is characterized by comprising the following steps: adding raw material graphite into a sulfuric acid solution of peroxide, standing for reaction, and then placing the mixture in an open manner to obtain a primary graphite three-dimensional structure; soaking, washing and drying the obtained primary graphite three-dimensional structure to obtain expandable graphite aerogel with residual sulfuric acid among layers; and (3) carrying out high-temperature thermal expansion on the obtained expandable graphite aerogel, wherein the temperature is 400-1000 ℃, and obtaining the macroscopic graphene aerogel. The method disclosed by the invention is simple and convenient to operate, low in energy consumption and high in efficiency, and is a method for preparing the graphene aerogel in a large scale. The graphene sheets of the obtained macroscopic graphene aerogel keep a high hexagonal crystal structure and inherit the inherent properties of graphene to the maximum extent; the obtained macroscopic graphene aerogel contains abundant and firm cross-linking points and has excellent structural stability, electron conduction performance and other performances.
Description
Technical Field
The invention belongs to the field of preparation of nano carbon materials, and particularly relates to a macroscopic graphene aerogel and a preparation method thereof.
Background
Graphene aerogel is a porous carbon material formed by graphene sheets that are lapped in three-dimensional space. The composite material has the characteristics of light weight, high temperature resistance, corrosion resistance, high specific surface area, high electric conductivity, high heat conductivity, high porosity and the like, and can be widely applied to the fields of pollutant adsorption, heat management, electric conductivity, electromagnetic shielding and wave absorption, pressure sensing, lithium battery electrode materials, heterogeneous catalysis and the like.
At present, the typical methods for preparing the graphene aerogel mainly include a chemical vapor deposition method and a sol-gel method. The aerogel prepared by the former has few graphene defects, but has extremely high cost and is difficult to produce in a large scale. The graphene with certain solution dispersibility is used as a raw material of the graphene, and comprises graphene oxide and liquid-phase exfoliated graphene under the stability of a surfactant. And due to the existence of the functional group and the surfactant, the continuity of the electric conduction network or the heat conduction network in the aerogel is greatly weakened, and the practical application of the aerogel is limited.
Therefore, the development of a method for preparing the high-performance graphene aerogel with low cost and large scale can greatly promote the development and practical application of the graphene aerogel in the fields of electrode materials, electric and heat conducting composite materials, electromagnetic shielding materials and the like.
Disclosure of Invention
In view of the above drawbacks of the prior art, an object of the present invention is to provide a macroscopic graphene aerogel and a preparation method thereof, which simultaneously solve the three problems of difficult scale-up, more graphene defects, and low specific surface area in the preparation of graphene aerogel.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a macroscopic graphene aerogel comprises the following steps:
adding raw material graphite into a sulfuric acid solution of peroxide, standing for reaction, then placing the mixture in an open manner, and further lapping graphene sheets to obtain a primary graphite three-dimensional structure;
step (2) soaking, washing and drying the primary graphite three-dimensional structure body obtained in the step (1) to obtain expandable graphite aerogel with residual sulfuric acid among layers;
and (3) performing high-temperature thermal expansion on the expandable graphite aerogel obtained in the step (2), wherein the temperature is 400-1000 ℃, so as to obtain the macroscopic graphene aerogel.
The relevant content in the technical scheme of the preparation method is explained as follows:
1. in the above scheme, the raw material graphite in step (1) is selected from one or more of thermal expansion graphite, flake graphite, artificial graphite (e.g. pyrolytic graphite), graphene powder, conductive carbon black, activated carbon and carbon nanotubes. When more than one raw material is selected, the graphene-based composite aerogel can be finally obtained.
2. In the scheme, the peroxide in the step (1) is one or more selected from the group consisting of peroxymonosulfuric acid, peroxydisulfuric acid, hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate.
3. In the scheme, the weight of the sulfuric acid solution of the peroxide is 10-500 times of that of the raw material graphite; the mass ratio of the sulfuric acid to the peroxide is 1-100: 1.
4. in the above scheme, in the step (1), the open air is left for 1 minute to 24 hours. The purpose of open placement is: a. in the open-mouth water absorption process, graphene sheets are further lapped; b. the sulfuric acid in the graphite worms can slowly absorb moisture in the air by being placed in an open manner, namely the method for slowly diluting the concentrated sulfuric acid can avoid violent exothermic vaporization when water is added in the step (2) to cause disintegration and damage of the primary graphite three-dimensional structure.
5. In the scheme, in the step (1), the standing reaction temperature is 0-130 ℃, and the standing time is 0.1-1 hour.
6. In the above scheme, in the step (3), the processing time of high-temperature thermal expansion is 1 to 300 seconds.
7. In the scheme, the macroscopic graphene aerogel has a multi-stage structure, the form of the multi-stage structure is that graphene sheets are lapped into a worm-shaped structure in a three-dimensional space, and the worm-shaped structures are firmly adhered through lapping of the graphene sheets. The specific surface area of the macroscopic graphene aerogel is 200-800 m2Has microporous, mesoporous and macroporous structures. The average number of graphene layers in the macroscopic graphene aerogel is 1-7.
The preparation method can be adopted to prepare the macroscopic graphene aerogel.
The method takes graphite as a raw material, and the graphite is expanded and peeled between sheets through chemical expansion to form vermicular graphite, and the vermicular graphite is spontaneously arranged to form close adhesion among graphite worms; and then, carrying out proper water washing and drying to obtain an expandable graphite three-dimensional structure containing residual intercalation agent, and carrying out high-temperature thermal expansion to obtain the macroscopic graphene aerogel with high specific surface area.
By adopting the above technology, compared with the prior art, the invention has the following advantages:
1. according to the method, cheap graphite is used as a raw material, and stripping and primary liquid phase assembly of graphene are completed simultaneously through chemical expansion. The graphene worms form arrangement and close adhesion, and a high-electric-conductivity high-heat-conductivity graphene network is constructed. In the chemical expansion techniques disclosed in the past, only the expansion peeling effect on graphite is noticed, and the arrangement and adhesion effect among worms which are peculiar to chemical expansion are ignored. It is particularly noted that the open placement operation of the present invention has two important features: (1) in the open placement, the sulfuric acid in the graphite worms slowly absorbs water, so that the graphene sheets are further lapped, and the slight contraction phenomenon of the volume of the graphite three-dimensional structure body can be observed in appearance; (2) avoids the damage of the nodes in the gel caused by the violent exothermic vaporization caused by the rapid dilution of the sulfuric acid in the water washing operation. The water absorption process in the open placement has important significance for the effective lap joint of the graphene sheets, and the close and abundant nodes greatly improve the electric and heat conduction performance of the graphene aerogel in the macroscopic scale.
2. According to the invention, the chemically expanded graphite after being washed with moderate water is innovatively used as the expandable graphite, and high-temperature thermal expansion is adopted for the expandable graphite, namely, interlayer sulfuric acid is rapidly released, so that further stripping of graphene sheets is realized, the macroscopic graphene aerogel with a high specific surface area is prepared, and the macroscopic performance of the graphene aerogel, such as electromagnetic shielding performance, is improved.
3. According to the invention, irreversible oxidation of graphene is not involved, and the complete hexagonal crystal form of graphene is maintained, so that the excellent properties of electric conductivity, heat conductivity, mechanics and the like of graphene are retained to the greatest extent.
4. The reaction process has no special requirements on containers and equipment, no release of toxic and harmful gases, and the problems of high energy consumption, difficult scale production and the like in the prior art are greatly solved.
5. The thickness of the hole wall in the macroscopic graphene aerogel is 1-7 layers, and the macroscopic graphene aerogel can bear the capillary force in the normal-pressure drying process. After the macroscopic graphene aerogel is dried under normal pressure, the volume of the macroscopic graphene aerogel does not shrink obviously. Compared with the vacuum freeze drying technology involved in the preparation of the graphene aerogel disclosed in the prior art, the method has the obvious cost advantage, and the macroscopic graphene aerogel can be dried by using a normal-pressure drying method with low cost.
In a word, the method is simple and convenient to operate, low in energy consumption and high in efficiency, and is a method capable of preparing the graphene aerogel in a large scale. The obtained macroscopic graphene aerogel has two advantages: (1) the graphene sheet retains a high hexagonal crystal structure and inherits the inherent properties of graphene to the maximum extent; (2) the high-strength high. Therefore, the material can be widely applied to the fields of high-performance electric and heat conduction materials, polymer composite materials, pollutant adsorption, energy storage devices, sensor materials and the like.
Drawings
Fig. 1 is a macroscopic photograph of the graphene aerogel, and it can be seen that graphene worms have an obvious arrangement structure.
Fig. 2 is a scanning electron microscope photograph of a microstructure of a graphene aerogel, in which stable cross-linking points are formed between graphene sheets, including between the inside of a worm and the worm; (a) and (b) represents an aerogel surface; (c) and (d) represents the aerogel interior. The scale bars in the figure are all 200 microns. FIG. 3 is a graph showing the relationship between the conductivity and the density of the graphene aerogel in the vertical direction during the compression process, wherein the graph shows that the conductivity is 18 mg/cm3The conductivity of the aerogel can reach 12S/cm.
Fig. 4 shows the electromagnetic shielding performance of the graphene aerogel. The test sample has an areal density of 3.3 mg/cm2Graphene aerogel with a thickness of 1.1 mm. In the X-band, the shielding effectiveness is 120-130 dB.
Detailed Description
The invention is further described with reference to the following figures and examples:
example 1: macroscopic graphene aerogel and preparation method thereof
Step (1), 10 g of ammonium persulfate is dissolved in 90 g of concentrated sulfuric acid.
And (2) adding 1 g of crystalline flake graphite into the solution in the step (1). The reaction was allowed to stand at 60 ℃ for 2 hours. And finally obtaining the primary graphite three-dimensional structure which absorbs the acid liquor and is about 400 cubic centimeters.
And (3) placing the primary graphite three-dimensional structure in the step (2) for 6 hours in an open mode, adding 500 ml of water to soak the primary graphite three-dimensional structure along the wall of the cup by using a dropper, pouring out the upper liquid after soaking for two hours, and then placing the primary graphite three-dimensional structure into a 70 ℃ oven for drying to obtain the expandable graphite aerogel with residual sulfuric acid between layers.
And (4) placing the expandable graphite aerogel in a muffle furnace at 800 ℃ for further expansion, wherein the treatment time is 60 seconds, and obtaining the macroscopic graphene aerogel. The nitrogen desorption test shows that the specific surface area is 800 m, referring to the attached figures 1 to 42(ii) in terms of/g. The thermal conductivity of the graphene paper obtained after calendering and densification reaches 840W/(K.m), and the electrical conductivity is 2800S/cm.
Example 2: macroscopic graphene aerogel and preparation method thereof
Step (1), 10 g of peroxymonosulfuric acid is dissolved in 90 g of concentrated sulfuric acid.
And (2) adding 1 g of thermal expansion graphite into the solution in the step (1). The reaction was allowed to stand at 60 ℃ for 2 hours. And finally obtaining the primary graphite three-dimensional structure which absorbs the acid liquor and is about 400 cubic centimeters.
And (3) placing the primary three-dimensional structure body in the step (2) for 6 hours in an open mode, adding 500 ml of water to soak the primary three-dimensional structure body along the wall of the cup by using a dropper, pouring out upper-layer liquid after soaking for two hours, and then placing the primary three-dimensional structure body into a 70 ℃ oven for drying to obtain the expandable graphite aerogel with residual sulfuric acid between layers.
And (4) further expanding the expandable graphite aerogel in a muffle furnace at 500 ℃ for 60 seconds to obtain the macroscopic graphene aerogel. The nitrogen desorption test shows that the specific surface area is 300 m2/g。
Example 3: macroscopic graphene aerogel and preparation method thereof
Step (1), 10 g of potassium persulfate is dissolved in 90 g of concentrated sulfuric acid.
And (2) adding 1 g of crystalline flake graphite and 0.5g of conductive carbon black into the solution in the step (1). The reaction was allowed to stand at 60 ℃ for 2 hours. And finally obtaining the primary graphite three-dimensional structure which absorbs the acid liquor and is about 400 cubic centimeters.
And (3) placing the primary three-dimensional structure body in the step (2) for 15 minutes in an open mode, adding 500 ml of water to soak the primary three-dimensional structure body along the wall of the cup by using a dropper, pouring out upper-layer liquid after soaking for two hours, and then placing the primary three-dimensional structure body into a 70 ℃ oven for drying to obtain the expandable graphite aerogel with residual sulfuric acid between layers.
And (4) placing the expandable graphite aerogel in a muffle furnace at 800 ℃ for further expansion, wherein the treatment time is 60 seconds, and obtaining the macroscopic graphene aerogel. The density was 4.5 mg/cm3The conductivity was 1.2S/cm. The thermal conductivity of the graphene paper obtained after calendering and densification reaches 500W/(K.m), and the electrical conductivity is 2000S/cm.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (4)
1. A preparation method of a macroscopic graphene aerogel is characterized by comprising the following steps:
adding raw material graphite into a sulfuric acid solution of peroxide, standing for reaction, then placing the mixture in an open manner, and further lapping graphene sheets to obtain a primary graphite three-dimensional structure; the open air is placed for 1 minute to 24 hours;
step (2) soaking, washing and drying the primary graphite three-dimensional structure body obtained in the step (1) to obtain expandable graphite aerogel with residual sulfuric acid among layers;
step (3) performing high-temperature thermal expansion on the expandable graphite aerogel obtained in the step (2), wherein the temperature is 400-1000 ℃, so as to obtain macroscopic graphene aerogel;
the raw material graphite in the step (1) is selected from one or two of thermal expansion graphite and flake graphite;
the peroxide in the step (1) is selected from one or more of peroxymonosulfuric acid, ammonium persulfate and potassium persulfate;
the macroscopic graphene aerogel has a multi-stage structure, the form of the multi-stage structure is that graphene sheets are lapped into a worm-shaped structure in a three-dimensional space, the worm-shaped structures are firmly adhered through lapping of the graphene sheets, and the macroscopic graphene aerogel contains micropores, mesopores and macropores.
2. The method for preparing a macroscopic graphene aerogel according to claim 1, characterized in that: the weight of the sulfuric acid solution of the peroxide is 10-500 times of that of the raw material graphite; the mass ratio of the sulfuric acid to the peroxide is 1-100: 1.
3. the method for preparing a macroscopic graphene aerogel according to claim 1, characterized in that: in the step (3), the processing time of high-temperature thermal expansion is 1-300 seconds.
4. The macroscopic graphene aerogel prepared according to the preparation method of any one of claims 1 to 3.
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