CN114933300B - Graphene foam support with high specific surface area - Google Patents

Graphene foam support with high specific surface area Download PDF

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CN114933300B
CN114933300B CN202210735354.5A CN202210735354A CN114933300B CN 114933300 B CN114933300 B CN 114933300B CN 202210735354 A CN202210735354 A CN 202210735354A CN 114933300 B CN114933300 B CN 114933300B
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graphene
coating
graphene foam
binder
preparing
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CN114933300A (en
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蔡金明
陈其赞
郝振亮
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Guangdong Morion Nanotech Co Ltd
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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
    • C01B32/194—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

Abstract

The invention belongs to the technical field of graphene materials, and provides a preparation method of a graphene foam scaffold. According to the preparation method provided by the invention, the carbonate and sodium bicarbonate salt are used as filling main materials, so that the acid solution is convenient to clean to obtain high porosity, and compared with the 3D graphene film, the preparation method has larger specific surface area and exposes more loadable sites; compared with the traditional preparation mode of graphene aerogel, the preparation method has the advantages of simple preparation process, suitability for large-scale industrial mass production, low manufacturing cost and the like.

Description

Graphene foam support with high specific surface area
Technical Field
The invention relates to the field of graphene materials, in particular to a graphene foam support with a high specific surface area.
Background
Graphene is a novel material with excellent optical, thermal, electrical, mechanical and other properties, and is widely focused by scientists. At present, commercial applications such as graphene heat conduction films, graphene temperature equalization plates and the like on electronic products of known brands such as Hua Cheng, millet and apple have been started in the field of thermal management, and attractive results are obtained in the field of electricity such as high-performance graphene conductive agents and research and development of graphene super capacitors. In many application fields, not only the electrical, thermal and other properties of graphene are considered, but also the high specific surface area of graphene is a factor of great concern. The graphene has ultrahigh specific surface area, and the high specific surface area can improve a large number of loading sites, so that the graphene has great application potential in the fields of high-loading application materials, such as photoelectrocatalysis, supercapacitors, material modification and the like. However, the high specific surface area of graphene is difficult to fully use in many times, mainly due to the layer-by-layer stacking, self-polymerization coating and the like of graphene, which results in a reduction of exposed loadable sites, such as self-polymerization film formation of graphene oxide, which greatly reduces the area of graphene that can be exposed to load, and graphene SP 2 Hybrid six-membered ring structures, the effective pore of which does not allow Li of minimum ionic radius + Through, more so to speak, small molecule materials.
In many applications, it is desirable that the reactive species be transported to active sites on the graphene surface for reaction. When small molecules or ions are transported and shuttled in the grapheme stacked layer by layer, the transportation distance of the lithium small molecules or ions can be greatly increased only along interlayer gaps and local holes of the grapheme, and the large steric hindrance phenomenon is shown, for example, when the grapheme conductive agent is applied to a lithium ion battery electrode, the film-shaped deposition of the grapheme on the surface of a pole piece is easily caused when the addition proportion of the grapheme conductive paste and the manufacturing process are in error, the transportation of lithium ions is greatly hindered, and the large steric hindrance effect is shown. Graphene can also be used to obtain 3D graphene with high specific surface area and less steric hindrance by certain means, such as graphene aerogel. However, the graphene aerogel preparation process is very long in load and duration, large in area cannot be prepared, low in efficiency, high in cost, poor in conductivity and incapable of fully exerting the electrical property of graphene. The invention provides a graphene foam support with high specific surface area, which can be prepared in a large area, and aims to solve the problem of steric hindrance of membranous graphene, so that a rapid channel for substance transportation is constructed during operation of membranous graphene, a loadable site of graphene is fully released, the application of graphene in the field of load application materials, such as photo-catalysis and electro-catalysis, is promoted, and a conductive support with high specific surface area and high load effect is provided for functional materials such as catalysis.
Disclosure of Invention
In order to solve the defects in the prior art, the primary aim of the invention is to provide a preparation method of a graphene foam support with high specific surface area, which mainly comprises the following steps:
and mixing the filling material with binder dispersion liquid, adding reduced graphene oxide, stirring and dispersing uniformly, coating to form a film, drying, and soaking in acid liquor to remove the filling material to obtain the graphene foam scaffold.
The preparation method comprises the following steps:
step 1: sodium carbonate or sodium bicarbonate which is subjected to drying and dewatering treatment is selected as a filling material; carbonate removed by the reaction of solution such as sodium carbonate, sodium bicarbonate and the like and acid liquor is selected as a filling main material of the high-surface-area graphene foam bracket, and the particle size of the filling main material can be selected according to the design pores of the graphene foam bracket.
Step 2: preparing a binder dispersion liquid, mixing the binder with a solvent, stirring and dispersing, wherein the stirring speed is set to 600-2000r/min, and preparing the binder dispersion liquid with the mass fraction of 0.1% -3%. According to the flexibility design requirement of the graphene foam support, selecting a binder, such as a rigid graphene foam support, selecting a binder such as a rigid PVDF, a CMC and the like, and selecting a binder such as a flexible PMMA, an epoxy resin and the like, or compounding the flexible and elastic graphene foam support. Selecting an oil auxiliary solvent such as NMP, DMF, xylene and the like according to the filling main material and the adhesive property; and selectively removing the filling carbonate in the membrane material by utilizing the characteristic that the oily binder is insoluble in water.
Step 3: preparing coating slurry, mixing 95% -99% of filling material and 0.1% -3% of binder according to mass percentage, fully and uniformly stirring, adding 0.1% -2% of graphene functional powder, and dispersing at high speed to obtain the coating slurry. And selecting graphene functional materials such as reduced graphene oxide powder, aminated graphene powder, element doped graphene powder, oxidized graphene powder and the like according to design requirements.
Step 4: coating to form a film, coating the coating slurry on a substrate after viscosity adjustment, and drying to obtain a coating layer; the specific mode of the viscosity adjustment is that the viscosity of the slurry is controlled within the range of 2000-10000 Pa.s by adding an auxiliary solvent in a proper amount. The prepared slurry is coated on PE, PET, PP or target substrate, or filled into a specific mold, and transferred to an oven at 60-150 ℃ for drying.
Step 5: immersing the dried sample in an acid solution with the mass fraction of 1-15%, removing carbonate filling main materials in the sample in an acid etching mode, washing with deionized water for multiple times, and drying to obtain the graphene foam bracket built by graphene and binder.
Step 6: the cut part of the sample was used for BET test to obtain specific surface area data of the sample, and the resistivity of the sample was measured using a four-probe resistance tester.
In a further technical scheme, before the filling material is added, the filling material needs to be baked for 2 hours at 80 ℃ to remove the moisture on the surface of the filling material.
In a further technical scheme, in the step of preparing the coating slurry, the graphene functional powder is placed in a vacuum drying oven at 150 ℃ for baking for at least 2 hours before being added, so as to remove moisture in the graphene functional powder and prevent sedimentation in the subsequent pulping process.
In a further technical scheme, in the coating film forming step, the thickness of the coating layer is XX-400 mu m.
In a further technical scheme, in the step of removing the filling material by soaking in acid liquor, hydrochloric acid with the mass fraction of 10% is selected as the acid liquor, the acid liquor is soaked until bubbles are not generated in the coating layer, the PH of the acid liquor is still acidic, the graphene foam scaffold is obtained, and the graphene foam scaffold is washed by deionized water and then dried.
Compared with the prior art, the invention has the following beneficial effects:
1. the graphene foam bracket with the high specific surface area provided by the invention has larger specific surface area compared with a 3D graphene film, exposes more loadable sites and is a load material with excellent performance.
2. Compared with a common oxide 3D porous support, the graphene foam support with the high specific surface area has more ideal conductive performance, can better conduct and excite carriers in the fields of photocatalysis, electrocatalysis and the like, and can be used as a loading material with the high specific surface area in the fields of photocatalysis and electrocatalysis.
3. According to the graphene foam bracket with the high specific surface area, the problem of steric hindrance of the layered graphene film is solved through a filling-etching strategy of a carbonate main material, and a rapid channel for transporting small molecular substances or ions is constructed by the remained gap; the carbonate and sodium bicarbonate salt are used as filling main materials, so that the acid solution is convenient to clean to obtain high porosity, the process is simple, the manufacturing cost is low, and the preparation with large area, controllable thickness and customized appearance can be carried out through coating and filling dies, so that the method is suitable for industrial production.
4. According to the graphene foam support with the high specific surface area, the proper binder can be selected according to design requirements to obtain the graphene foam support with different softness of flexibility and rigidity, the pores of the graphene foam support can be controlled by selecting the particle size of the filling material to obtain the graphene foam support with different pore sizes, the graphene foam support can be directly constructed on a target substrate, the graphene foam support can also be independently used, the graphene foam support has value in various places, and the application requirements of various actual scenes can be met.
Drawings
Fig. 1 is an SEM image of a graphene foam scaffold sample with a high specific surface area.
Fig. 2 is an SEM image of a graphene foam scaffold sample with a high specific surface area provided by the invention.
Fig. 3 is a BET test result of a graphene foam scaffold sample with a high specific surface area provided by the present invention.
Fig. 4 is a graphene foam scaffold sample obtained in example 3.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
The following are the specific examples section:
example 1
The invention provides a preparation method of a graphene foam bracket with high specific surface area, which comprises the following specific steps:
1) D is selected for 50 Sodium bicarbonate of =5 μm as a filling master material of the high surface area graphene foam scaffold, and baking the filling master material at 80 ℃ for 2 hours, with the aim of removing sodium bicarbonate surface moisture;
2) PVDF-5130 powder is selected as a binder, NMP is used as a solvent, and a digital display stirrer is used for stirring and dispersing under the condition of 600-2000r/min, so that the PVDF powder is fully dissolved, and PVDF dispersion solution with the mass fraction of 4% is prepared for standby;
3) NMP is selected as an auxiliary solvent according to the properties of the filling main material and the binder for subsequent auxiliary mixing;
4) Selecting common reduced graphene oxide powder as a functional material of a graphene foam bracket, and placing the reduced graphene oxide powder in a vacuum drying oven at 150 ℃ for baking for more than 2 hours so as to remove moisture in the reduced graphene oxide powder and prevent sedimentation in the subsequent pulping process;
5) Diluting the PVDF dispersion solvent with the mass fraction of 4% prepared in the step 2) into a PVDF dilution solution with the mass fraction of 1% by using NMP, and adding the D with the mass fraction of 98.5% after high-speed dispersion 50 After the main material is filled with sodium bicarbonate of which the thickness is equal to 5 mu m and fully and uniformly stirred, 0.5 mass percent of reduced graphene oxide powder is added, the reduced graphene oxide powder is dispersed at a high speed until the slurry is smooth and has no granular feel, and the viscosity of the slurry is controlled to 4000 mPa.S by adding an appropriate amount of NMP solvent subsequently.
6) Selecting a PET film as a coating substrate, wiping the PET film cleanly by using dust-free cloth, coating a coating layer with the thickness of 400 mu m on the PET film by using a four-side coater, and transferring a sample to an oven at 80 ℃ for drying after the coating is finished;
7) Immersing the dried sample in the prepared hydrochloric acid solution with the mass fraction of 10% for 2 hours, removing sodium bicarbonate filling main material in the sample in a hydrochloric acid etching mode until bubbles are not generated in the sample, and determining that the reaction is finished when the solution is still not acidic after the PH test paper test reaction. And (3) washing with deionized water until the PH value of the solution is neutral, then transferring the residual moisture absorbed by dust-free paper at the edge of the graphene foam bracket to a vacuum oven at 80 ℃ for low-pressure drying, and obtaining the graphene foam bracket built by graphene and a binder.
8) BET test is carried out on the sample of the cutting part by a static capacity method, the test result is shown in figure 3, and the obtained graphene foam scaffold sample is shown as a single-point BET with 466.404m 2 The specific surface area per gram, the resistivity of the graphene foam bracket is 22.3mΩ & cm by using a four-probe resistance tester, and the microstructure is a structure similar to a sponge and is similar to a membranous 3D stoneThe graphene membrane layer-by-layer stacked structure has the essential difference, can construct a rapid channel for transporting small molecules and ions, is a conductive load support material with high specific surface area, and has great application potential in the application fields of load materials such as photocatalysis, electrocatalysis, adsorption and the like. A portion of the sample was taken and observed under an electron microscope, as shown in fig. 1 and 2, and the sodium bicarbonate filler in the graphene foam scaffold left a large number of cavities after acid washing.
Example 2
This example differs from example 1 in that step 5) was performed by diluting the PVDF binder solution with NMP solvent to a PVDF dispersion solution of 0.2 mass%, and the other steps were the same as in example 1, with the purpose of exploring the effect of the PVDF binder addition amount on the graphene foam scaffold performance. The results showed that the specific surface area of the sample was only 172.3m 2 And/g, the resistivity of the sample is 55.6mΩ & cm, which is attributable to insufficient binder in the sample, collapse of the internal structure, and a large number of bubbles generated in the acid washing overweight break the connection of graphene, so that multipoint electrical conduction break points appear between the sheets, and the resistivity of the sample is high.
Example 3
The present example differs from example 1 in that step 5) was not diluted with NMP solvent, and PVDF dispersant of 4% mass fraction prepared in step 2) was directly used as an auxiliary solvent, and the other steps were the same as in example 1, with the purpose of exploring the effect of PVDF binder addition on graphene foam scaffold performance.
Samples prepared by the methods of examples 1-3 were taken, and a portion of the samples were cut for BET testing and resistivity testing using a four-probe resistance tester, with the test results shown in the following table:
examples PVDF mass percent Specific surface area Resistivity of
1 1% 466.4m 2 /g 22.3mΩ.cm
2 0.2% 172.3m 2 /g 55.6mΩ.cm
3 4% 250.5m 2 /g 118.7mΩ.cm
The above test data show that the graphene foam scaffold samples prepared by the method of example 1 have > 400m 2 According to the specific surface area/g, the resistivity of the graphene foam support is 22.3mΩ & cm by using a four-probe resistance tester, the microstructure is similar to a sponge structure, is essentially different from a membranous 3D graphene film layer-by-layer stacked structure, can construct a rapid channel for transporting small molecules and ions, is a conductive load support material with high specific surface area, and has great application potential in the application fields of load materials such as photocatalysis, electrocatalytic and adsorption. The test results of the samples prepared by the method of example 2 show that the graphene foam scaffold structure obtained by the adding proportion of PVDF binder of 0.2% mass fraction has collapse and local macropore phenomenon, and the BET test result is 172.3m 2 Per g, which is attributable to the inability to support when the binder addition is insufficientThe reduced graphene oxide builds a 3D porous graphene foam support, so that hole collapse occurs locally, and redundant reduced graphene oxide is stacked and deposited on the surface of a sample. The test results of the sample prepared by the method of example 3 show that the graphene foam scaffold obtained by the adding proportion of PVDF binder of 4% mass fraction is harder, and the BET test result is 250.5m 2 The resistivity test result was 118.7mΩ.cm, and a portion of the sample was taken under an electron microscope for observation, and the microstructure was similar to that of a sponge, as shown in fig. 4. In combination with the observed SEM images and test results, this is attributable to the fact that the excess binder addition, while better able to construct a 3D porous graphene foam scaffold, too much binder reduces the exposable loading sites of graphene, reduces the specific surface area, while the non-conductive binder also increases the resistivity of the sample.
Example 4
1) D is selected for 50 Sodium bicarbonate of =5 μm as a filling master material of the high surface area graphene foam scaffold, and baking the filling master material at 80 ℃ for 2 hours, with the aim of removing sodium bicarbonate surface moisture;
2) PVDF-900 powder is selected as a binder, NMP is used as a solvent, and a digital display stirrer is used for stirring and dispersing under the condition of 600-2000r/min, so that the PVDF powder is fully dissolved, and PVDF dispersion solution with the mass fraction of 4% is prepared for standby;
3) NMP is selected as an auxiliary solvent according to the properties of the filling main material and the binder for subsequent auxiliary mixing;
4) Selecting common reduced graphene oxide powder as a functional material of a graphene foam bracket, and placing the reduced graphene oxide powder in a vacuum drying oven at 150 ℃ for baking for more than 2 hours so as to remove moisture in the reduced graphene oxide powder and prevent sedimentation in the subsequent pulping process;
5) Diluting the PVDF dispersion solvent with the mass fraction of 4% prepared in the step 2) into a PVDF dilution solution with the mass fraction of 1% by using NMP, and adding the D with the mass fraction of 98.5% after high-speed dispersion 50 Sodium bicarbonate filling main material with the mass fraction of 5 mu m, adding 0.5% of reduced graphene oxide powder after fully and uniformly stirring, and separating at high speedThe state of the slurry is smooth and has no granular feel after being dispersed, and the viscosity of the slurry is controlled to 4000 mPa.S by adding an appropriate amount of NMP solvent subsequently;
6) Selecting a PET film as a coating substrate, wiping the PET film cleanly by using dust-free cloth, coating a coating layer with the thickness of 400 mu m on the PET film by using a four-side coater, and transferring a sample to an oven at 80 ℃ for drying after the coating is finished;
7) Immersing the dried sample in the prepared hydrochloric acid solution with the mass fraction of 10% for 2 hours, removing sodium bicarbonate filling main material in the sample in a hydrochloric acid etching mode until bubbles are not generated in the sample, and determining that the reaction is finished when the solution is still not acidic after the PH test paper test reaction. And (3) washing with deionized water until the PH value of the solution is neutral, then transferring the residual moisture absorbed by dust-free paper at the edge of the graphene foam bracket to a vacuum oven at 80 ℃ for low-pressure drying, and obtaining the graphene foam bracket built by graphene and a binder.
This example differs from example 1 in that PVDF-900 was used instead of PVDF-5130 binder in example 1 (both materials are conventional materials, both purchased from Cantonese light energy technologies Co., ltd.) and the other steps were the same as example 1, with the aim of exploring the effect of the size of the binder molecular weight on the performance of the graphene foam scaffold. The results show that when PVDF-900 is used as a binder, the obtained graphene foam scaffold is soft and has certain elasticity, and the BET test result is 287.7m 2 The resistivity test result was 33.4mΩ.cm, which is attributable to the fact that the intrinsic properties of the binder such as molecular weight are important factors affecting the properties of the sample, and the lower molecular weight, although the number of the obtained binder molecules is large, there is also a phenomenon of uneven connection, resulting in an increase in the resistivity of the sample.
Example 5
1) D is selected for 50 Sodium bicarbonate of =5 μm as a filling master material of the high surface area graphene foam scaffold, and baking the filling master material at 80 ℃ for 2 hours, with the aim of removing sodium bicarbonate surface moisture;
2) PVDF-5130 powder is selected as a binder, NMP is used as a solvent, and a digital display stirrer is used for stirring and dispersing under the condition of 600-2000r/min, so that the PVDF powder is fully dissolved, and PVDF dispersion solution with the mass fraction of 4% is prepared for standby;
3) NMP is selected as an auxiliary solvent according to the properties of the filling main material and the binder for subsequent auxiliary mixing;
4) Selecting common reduced graphene oxide powder as a functional material of a graphene foam bracket, and placing the reduced graphene oxide powder in a vacuum drying oven at 150 ℃ for baking for more than 2 hours so as to remove moisture in the reduced graphene oxide powder and prevent sedimentation in the subsequent pulping process;
5) Diluting the PVDF dispersion solvent with the mass fraction of 4% prepared in the step 2) into a PVDF dilution solution with the mass fraction of 1% by using NMP, and adding the D with the mass fraction of 98.5% after high-speed dispersion 50 After the main material is filled with sodium bicarbonate of which the thickness is equal to 5 mu m and fully and uniformly stirred, 0.5 mass percent of reduced graphene oxide powder is added, the reduced graphene oxide powder is dispersed at a high speed until the slurry is smooth and has no granular feel, and the viscosity of the slurry is controlled to 4000 mPa.S by adding an appropriate amount of NMP solvent subsequently.
6) A cube mould with the height of 1cm is used, the upper part of the mould is opened, the sizing agent prepared in the step 5 is poured into the mould until the height of the sizing agent is just flush with the height of the mould, and the sample is transferred into an oven at 80 ℃ for drying after pouring;
7) Immersing the dried sample in the prepared hydrochloric acid solution with the mass fraction of 10% for 2 hours, removing sodium bicarbonate filling main material in the sample in a hydrochloric acid etching mode until bubbles are not generated in the sample, and determining that the reaction is finished when the solution is still not acidic after the PH test paper test reaction. And (3) washing with deionized water until the PH value of the solution is neutral, then transferring the residual moisture absorbed by dust-free paper at the edge of the graphene foam bracket to a vacuum oven at 80 ℃ for low-pressure drying, and obtaining the graphene foam bracket built by graphene and a binder.
The difference between this example and example 1 is that step 6) uses a self-made 1cm high cube mold instead of PET film as the carrier substrate for pouring, and the other steps are the same as example 1, with the aim of exploring the effect of the coating thickness on the sample properties. The results show that the data obtained from the above-mentioned method,the surface of the obtained sample had a dent collapse, and the BET test result was 144.6m 2 And/g, which is attributable to the collapse of the surface layer structure caused by the gravity of the coating itself and the volatilization of the solvent when the thickness of the coating is large.
Example 6
The difference between this example and example 5 is that the mold, after the slurry is poured, is immersed in absolute ethanol to exchange solvent, part of NMP in the sample is replaced, PVDF is not dissolved in absolute ethanol, the whole structure of the sample is not affected, and then the sample is dried, and other steps are the same as in example 5, so that the effect of solvothermal volatilization on the structure of the sample is investigated. The structure shows that the concave collapse of the surface of the obtained sample is greatly relieved, and the BET test result is 307.2m 2 And/g, which is attributable to the effect of solvothermal volatilization on the structural surface, which can lead to collapse of the structural surface.
Example 7
This example differs from example 1 in that PMMA was used instead of PVDF binder in example 1, and the other steps were the same as in example 1, with the aim of exploring the effect of different binders on sample properties. The results show that the graphene foam scaffold obtained when PMMA is used as the binder has certain flexibility relative to the PVDF binder, and the appearance is still ensured to be kept as original after 500 bending experiments, which is attributable to the fact that the flexibility of the graphene foam scaffold is mainly determined by the intrinsic characteristics of the binder.

Claims (5)

1. A preparation method of a graphene foam scaffold is characterized by comprising the following steps: the method comprises the following steps:
(1) Sodium carbonate or sodium bicarbonate which is subjected to drying and dewatering treatment is selected as a filling main material;
(2) Preparing a binder dispersion liquid, namely, PVDF is used as a binder, NMP is used as a solvent, PVDF and NMP are mixed and stirred for dispersion, the stirring speed is set to 600-2000r/min, and PVDF dispersion liquid with the mass fraction of 0.2% -3% is prepared for standby;
(3) Preparing coating slurry, mixing 95% -99% of filling main materials and 0.1% -3% of binders according to mass percentage, fully and uniformly stirring, adding 0.1% -2% of graphene functional powder, and dispersing at a high speed to obtain the coating slurry; the graphene functional powder is reduced graphene oxide;
(4) Coating to form a film, coating the coating slurry on a substrate after viscosity adjustment, and drying to obtain a coating layer;
(5) And (3) soaking in acid liquor to remove the filling main material, soaking the coating layer in the acid liquor, and removing the filling main material through the acid liquor to obtain the graphene foam bracket constructed by graphene and the binder.
2. The method for preparing the graphene foam scaffold according to claim 1, which is characterized by comprising the following steps: the filling main material needs to be baked for 2 hours at 80 ℃ before being added.
3. The method for preparing the graphene foam scaffold according to claim 1 or 2, which is characterized in that: in the step of preparing the coating slurry, the graphene functional powder is placed in a vacuum drying oven at 150 ℃ for at least 2 hours before being added, so as to remove the moisture in the graphene functional powder.
4. The method for preparing the graphene foam scaffold according to claim 1 or 2, which is characterized in that: in the coating and film forming step, the concentration of the coating slurry is controlled to be 2000-10000 mPas by adding a solvent, the drying temperature after coating is set to be 80 ℃, the thickness of the coating layer is 400 mu m, and the substrate is selected from any one of PE, PET or PP.
5. The method for preparing the graphene foam scaffold according to claim 1 or 2, which is characterized in that: in the step of soaking in acid liquor to remove the filling main material, the acid liquor is hydrochloric acid with the mass percent of 10%, the acid liquor is soaked until bubbles are not generated in the coating layer, the pH value of the acid liquor is still acidic, the graphene foam scaffold is obtained, and the graphene foam scaffold is washed by deionized water and then dried.
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US9966199B2 (en) * 2016-01-11 2018-05-08 Nanotek Instruments, Inc. Supercapacitor having highly conductive graphene foam electrode
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US11420872B2 (en) * 2018-05-31 2022-08-23 Global Graphene Group, Inc. Graphene foam-based sealing materials
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