CN108530073B - Preparation method of flexible self-supporting three-dimensional porous graphene membrane - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 96
- 239000012528 membrane Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
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- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000004377 microelectronic Methods 0.000 abstract description 2
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- 239000003990 capacitor Substances 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 230000005012 migration Effects 0.000 description 1
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- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/522—Graphite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/067—Macromolecular compounds
Abstract
The invention provides a preparation method of a flexible self-supporting three-dimensional porous graphene membrane, which comprises the steps of selecting a high molecular polymer with poor thermal stability as a template agent, blending the template agent with graphene oxide, carrying out suction filtration to form a membrane, and carrying out high-temperature heat treatment under the protection of inert gas. In the high-temperature heat treatment process, the graphene oxide is reduced into graphene, and the high-molecular polymer with poor thermal stability is completely decomposed to leave developed pores, so that the flexible self-supporting three-dimensional porous graphene membrane is obtained, the thickness of the membrane can be controlled within the range of 5-100um, the pore size is within the range of 5-100nm, and the specific surface area is 300-1600 m-2(ii) in terms of/g. The pore shape, size and porosity of the prepared flexible self-supporting three-dimensional porous graphene membrane can be conveniently regulated and controlled through the morphology (such as linear, spherical and columnar), molecular weight and dosage of the high-molecular polymer template. The material can be applied to the fields of flexible super capacitors, flexible batteries, microelectronics, ion adsorption, membrane separation and the like.
Description
Technical Field
The invention relates to a preparation method of a flexible self-supporting three-dimensional porous graphene membrane.
Background
Graphene is a novel two-dimensional nano carbon material, and has high specific surface area, conductivity and strength. The graphene nanosheets can self-assemble under the action of van der waals force to form a flexible graphene film. The flexible membrane has strong mechanical property, and the special structure and unique property make the flexible membrane have wide application prospect in the fields of material science, flexible energy storage, microelectronics, membrane separation and the like. At present, the method for preparing graphene films in laboratories is mainly to prepare graphene oxide films by a vacuum filtration method and then obtain graphene films by chemical reduction or thermal reduction. The stacking of graphene sheet layers leads the actual specific surface of graphene to be far lower than the theoretical value, thereby influencing the application of graphene in the aspects of electrochemical energy storage, ion adsorption and the like. The porous structure can improve the specific surface of the material, shorten an ion migration path and contribute to improving the performances of graphene in electrochemical energy storage and ion adsorption. At present, multiple methods are reported for preparing porous graphene, for example, a hydrothermal self-assembly method and a Chemical Vapor Deposition (CVD) method using a foam metal as a template can prepare graphene with a three-dimensional structure, and graphene nanosheets are etched by using a strong alkali KOH activation method, a phosphoric acid activation method, a carbon dioxide activation method and the like to obtain powdery graphene with a porous structure. However, the research on the flexible porous graphene film has no mature method at present, the flexible graphene film generally depends on the close stacking of two-dimensional nanosheets to form a film, and how to introduce a porous structure into the structure of the flexible graphene on the premise of keeping the flexibility and the strength is a challenge.
Disclosure of Invention
The invention aims to provide a preparation method of a flexible self-supporting three-dimensional porous graphene membrane. The obtained porous graphene flexible membrane has good flexibility and strength, controllable pore morphology, high specific surface and high conductivity, has the advantages of two-dimensional nano materials and porous materials, and has great significance for the application of the graphene membrane in the field of material science.
The invention provides a preparation method of a flexible self-supporting three-dimensional porous graphene membrane, which is characterized by comprising the following steps: taking a high molecular polymer with poor thermal stability as a template agent, uniformly dispersing the template agent and a graphene oxide solution, carrying out vacuum filtration to form a film, and then carrying out high-temperature pyrolysis under the protection of an inert atmosphere to prepare a flexible self-supporting three-dimensional porous graphene film; the high molecular polymer is one or more of polyvinyl alcohol (PVA), polyethylene glycol (PEG), polymethyl methacrylate (PMMA), Polystyrene (PS) and polyvinylpyrrolidone (PVP); a molecular weight in the range of 5000 to 100000; the method comprises the following steps
(1) Preparing graphene oxide into an aqueous solution with the concentration of 0.5-10 mg/mL;
(2) dispersing the high molecular polymer in deionized water, wherein the concentration is 5-50 mg/mL;
(3) mixing the solution (2) and the solution (1) according to a certain proportion, stirring and carrying out ultrasonic treatment to uniformly disperse the two solutions;
(4) vacuum filtering the mixed solution (3) to form a film, and drying to obtain a graphene oxide and high polymer composite film;
(5) heating the graphene oxide and high polymer composite membrane to 400-1000 ℃ under the protection of inert gas, and carrying out constant-temperature heat treatment for 2-8h to obtain the flexible self-supporting three-dimensional porous graphene membrane.
The invention also provides a flexible self-supporting three-dimensional porous graphene membrane which is characterized in that the graphene membrane has a honeycomb three-dimensional network porous structure and good flexibility, the thickness of the membrane can be controlled within the range of 5-100um, the pore size is 2-100nm, and the specific surface area is 300-1600 m-2/g。
Wherein the mass ratio of the high molecular polymer and the graphene oxide in the step (3) is (0.1-10): 1.
And (3) the inert gas in the step (5) is any one or a mixture of several of nitrogen, argon, helium and neon.
The flexible self-supporting three-dimensional porous graphene membrane is prepared by adopting a blending carbonization method in one step, and the principle of the method is that in the high-temperature heat treatment process, the thermal reduction of graphene oxide and the thermal degradation of a polymer are carried out simultaneously, the graphene oxide is reduced into graphene, and a high polymer with poor thermal stability is completely decomposed to leave developed pores, so that the flexible self-supporting three-dimensional porous graphene membrane is obtained. In addition, the method is not limited to organic polymers, is also suitable for inorganic polymers and inorganic nanoparticles which are difficult to dissolve, and can obtain the porous graphene film by high-temperature treatment under the protection of inert gas and template removal.
Compared with the closest prior art, the technical scheme provided by the invention has the following remarkable advantages:
the invention uses the high molecular polymer with poor thermal stability as the template agent to prepare the porous graphene membrane for the first time, and the porous graphene membrane has high specific surface and developed pore structure. The pore structure is uniform and controllable, the morphology and the size of pores are controlled by selecting polymers with different linear or spherical structures, and the porosity can be regulated and controlled by adjusting the proportion of the polymers and the graphene oxide;
2, the thermal reduction of the graphene oxide and the pyrolysis of the polymer template are synchronously carried out, the porous graphene is directly obtained after the thermal treatment, and compared with the traditional operation of firstly preparing the graphene and then constructing a porous structure, the scheme has the advantages of simple preparation process and low energy consumption;
3 the thickness of the porous graphene membrane can be regulated and controlled by adding the amount of the graphene oxide and the polymer, has a loose structure and excellent ionic conductivity, and can be applied to electrochemical energy storage, adsorption, catalysts and catalyst carriers.
Description of the drawings:
fig. 1 is an SEM of the graphene oxide and spherical PS composite film in example 2, and it can be seen that the film thickness is about 50 um;
fig. 2 is a partially enlarged SEM of the graphene oxide and spherical PS composite film in example 2, in which graphene oxide nanosheets are uniformly wrapped on the PS surface;
fig. 3 is an SEM of the graphene porous membrane after heat treatment in example 2, and it can be seen that the membrane still has good integrity, and the structure built by the two does not collapse during the heat treatment, and the membrane thickness is about 50 um;
fig. 4 is a partially enlarged SEM of the porous graphene film after heat treatment in example 2, with PS decomposed, and the porous morphology built up by graphene sheets was well maintained.
The specific implementation mode is as follows:
the technical solutions provided by the present invention are further clearly and completely illustrated by the following specific examples, which are not intended to limit the present invention.
Example 1
(1) Preparing graphene oxide into a 0.5 mg/mL graphene oxide aqueous solution;
(2) adding linear PVA with the molecular weight of 5000 into deionized water, and stirring and dissolving at the temperature of T =60 ℃ to prepare a PVA solution with the concentration of 5 mg/mL;
(3) mixing 100 mL of graphene oxide aqueous solution with 1mL of PVA solution, stirring and carrying out ultrasonic treatment to uniformly disperse the two solutions;
(4) vacuum filtering the mixed solution to form a film, and drying to obtain a graphene oxide and PVP composite film;
(5) heating the graphene oxide and PVP composite membrane to 400 ℃ under the protection of nitrogen gas, and carrying out constant-temperature heat treatment for 8 hours to obtain the flexible self-supporting three-dimensional porous graphene membrane.
Example 2
(1) Preparing graphene oxide into a graphene oxide aqueous solution of 1 mg/mL;
(2) adding spherical PS with the molecular weight of 10000 into deionized water, and performing ultrasonic dispersion to prepare a PS solution with the concentration of 50 mg/mL;
(3) mixing 100 mL of graphene oxide aqueous solution with 2 mL of PS solution, stirring and ultrasonically treating the mixture to uniformly disperse the two solutions;
(4) vacuum filtering the mixed solution to form a film, and drying to obtain a graphene oxide and PS composite film (shown in figures 1 and 2 as SEM of the graphene oxide and PS composite film, wherein figure 1 is a macroscopic morphology figure, and figure 2 is a partially enlarged view);
(5) heating the graphene oxide and PS composite membrane to 800 ℃ under the protection of argon gas, and carrying out constant-temperature heat treatment for 2 h to obtain the flexible self-supporting three-dimensional porous graphene membrane (as shown in SEM of the porous graphene membrane shown in figures 3 and 4, wherein figure 3 is a macro topography and figure 4 is a partial enlarged view).
Example 3
(1) Preparing graphene oxide into a 10mg/mL graphene oxide aqueous solution;
(2) adding spherical PMMA with the molecular weight of 100000 into deionized water, and performing ultrasonic dispersion to prepare a PMMA solution with the concentration of 10 mg/mL;
(3) mixing 1mL of graphene oxide aqueous solution with 10 mL of PMMA solution, stirring and ultrasonically dispersing the two solutions uniformly;
(4) vacuum filtering the mixed solution to form a film, and drying to obtain a graphene oxide and PMMA composite film;
(5) heating the graphene oxide and PMMA composite film to 500 ℃ under the protection of helium gas, and carrying out constant-temperature heat treatment for 6h to obtain the flexible self-supporting three-dimensional porous graphene film.
Example 4
(1) Preparing 5 mg/mL graphene oxide aqueous solution from graphene oxide;
(2) adding linear PEG with the molecular weight of 80000 into deionized water, and performing ultrasonic dispersion to prepare a PEG solution with the concentration of 5 mg/mL;
(3) mixing 20 mL of graphene oxide aqueous solution with 10 mL of PEG solution, stirring and ultrasonically treating to uniformly disperse the two solutions;
(4) vacuum filtering the mixed solution to form a film, and drying to obtain a graphene oxide and PEG composite film;
(5) and heating the graphene oxide and PEG composite membrane to 700 ℃ under the protection of neon gas, and carrying out constant-temperature heat treatment for 6h to obtain the flexible self-supporting three-dimensional porous graphene membrane.
Claims (2)
1. A preparation method of a flexible self-supporting three-dimensional porous graphene membrane is characterized by comprising the following steps: taking a high molecular polymer as a template agent, carrying out ultrasonic dispersion on the high molecular polymer and graphene oxide in a solvent uniformly, carrying out vacuum filtration to form a film, and then carrying out high-temperature heat treatment under the protection of an inert atmosphere to prepare a flexible self-supporting three-dimensional porous graphene film; the high molecular polymer is one or more of polyvinyl alcohol, polyethylene glycol, polymethyl methacrylate, polystyrene and polyvinylpyrrolidone; the molecular weight of the high molecular polymer is in the range of 5000 to 100000; the method comprises the following steps:
(1) preparing graphene oxide into an aqueous solution with the concentration of 0.5-10 mg/mL;
(2) dispersing the high molecular polymer in deionized water, wherein the concentration is 5-50 mg/mL;
(3) mixing the solution (2) and the solution (1) according to a certain proportion, stirring and carrying out ultrasonic treatment to uniformly disperse the high molecular polymer and the graphene oxide;
(4) vacuum filtering the mixed solution (3) to form a film, and drying to obtain a graphene oxide and high polymer composite film;
(5) heating the graphene oxide and high-molecular polymer composite membrane to 400-1000 ℃ under the protection of inert gas, and carrying out constant-temperature heat treatment for 2-8h to obtain a flexible self-supporting three-dimensional porous graphene membrane; the graphene membrane has a honeycomb three-dimensional network porous structure and good flexibility, the thickness of the membrane is controlled within the range of 5-100um, the pore size is 2-100nm, and the specific surface area is 300-1600m2/g。
2. The method for preparing the flexible self-supporting three-dimensional porous graphene membrane according to claim 1, wherein the mass ratio of the high molecular polymer to the graphene oxide in the step (3) is (0.1-10): 1.
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| CN106968128A (en) * | 2017-04-12 | 2017-07-21 | 株洲时代新材料科技股份有限公司 | A kind of soft graphite alkenyl extrusion coating paper and its preparation method and application |
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