CN111484002B - Preparation method and application of porous graphene film - Google Patents
Preparation method and application of porous graphene film Download PDFInfo
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- CN111484002B CN111484002B CN202010305233.8A CN202010305233A CN111484002B CN 111484002 B CN111484002 B CN 111484002B CN 202010305233 A CN202010305233 A CN 202010305233A CN 111484002 B CN111484002 B CN 111484002B
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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- 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
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- 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
The invention discloses a preparation method and application of a porous graphene film, graphene is generated by an in-situ method, a carbon precursor is carbonized at high temperature, then metal oxide is reduced into simple substance by carbon, and then metal catalytic carbon is changed into graphene.
Description
Technical Field
The invention relates to a graphene film, in particular to a preparation method and application of a porous graphene film; belongs to the technical field of carbon materials.
Background
Graphene (Graphene) is a material consisting of carbon atoms in sp 2 The hybridized orbit forms a hexagonal two-dimensional carbon nanomaterial with honeycomb lattice. Has excellent optical, electrical and mechanical properties, is widely applied to a plurality of fields such as mechanics, electricity and biology, and has wide application prospect especially in the field of nano materials.
In the prior art, in the preparation process of the graphene film, the main raw material adopted is graphene oxide, but the cost of the graphene oxide is too high, so that the graphene film product lacks market competitiveness and cannot be widely popularized, and the application field of the graphene film product is greatly limited. For example, the invention patent with application number 201810715882.8 discloses a preparation method of a heterostructure porous graphene oxide film, a graphene film and a generator, wherein the preparation method of the heterostructure porous graphene oxide film is as follows: firstly, freeze-drying a graphene oxide solution to prepare the graphene oxide aerogel; then heating and reducing the graphene oxide aerogel from the bottom to obtain partially reduced graphene oxide aerogel at the bottom; and finally, applying pressure to the graphene oxide aerogel partially reduced at the bottom in the vertical direction to obtain the heterostructure porous graphene oxide film. According to the method, the heterostructure porous graphene oxide film is obtained through freeze drying of a graphene oxide solution, bottom heating reduction and vertical pressure application. However, as previously mentioned, the high cost of raw materials and processes results in a product that lacks market competitiveness.
In view of this, it is necessary to develop a new preparation method of porous graphene film in order to simplify the process, reduce the cost, and thus improve the market competitiveness of the product.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a preparation method and application of a porous graphene film, and the porous graphene film is obtained by adopting the preparation method of generating graphene in situ, so that the cost is greatly reduced.
In order to achieve the above object, the present invention adopts the following technical scheme:
the invention firstly discloses a preparation method of a porous graphene film, which comprises the following steps:
s1, preparing a precursor mixture: uniformly mixing a template agent, a carbon precursor and a solvent to prepare a precursor mixture; the template agent is also a catalyst for catalyzing and forming graphene;
s2, forming a mixture film layer prepared in the step S1 on the substrate;
s3, drying to remove the solvent in the mixture to form an embryo membrane;
s4, catalyzing carbon in the carbon precursor in situ to generate graphene;
s5, removing the template to obtain the porous graphene film, wherein the thickness of the graphene film can be adjusted within the range of 100 nanometers to 1 centimeter according to the requirement.
The membrane obtained by the method comprises a three-dimensional porous open network which is connected with each other, and the pore diameter can be adjusted within the range of 2 nm-10 um.
Preferably, the carbon precursor is a substance capable of generating carbon at high temperature, and is selected from one or more of pitch, carbohydrate, alcohol, preferably mesophase pitch, and naphthalene-based pitch, coal-based pitch, or petroleum-based pitch. The solvent is one of water, acetone or alcohol, the mass fraction of the solvent is 40% -90%, and the dosage of the solvent can be adjusted according to the consistency of the precursor mixture.
More preferably, the template agent is selected from one of inorganic particles such as iron oxide, ferroferric oxide, nickel oxide and cobalt oxide, and the template agent is reduced by carbon into metal simple substance (carbon reduces the metal oxide into simple substance) in the high-temperature carbonization process of the subsequent step S4, and the metal simple substance catalyzes the conversion of carbon into graphene. It should be particularly noted that the templating agent should not react with the carbon precursor in the previous steps S1-S3.
Preferably, in the aforementioned step S4, the template is caused to catalyze carbon to generate graphene by a high-temperature heat treatment. The heat treatment temperature is 600-1000 ℃, and the heat treatment time is 1-24 h.
More preferably, the heat treatment is performed in a protective atmosphere of nitrogen, helium, argon or a mixed gas thereof in order to prevent the oxidation reaction.
As another preferable mode, the template agent is ferric chloride and ammonia water, ferric hydroxide is generated in situ through chemical reaction, ferric oxide is generated through subsequent pyrolysis, then carbon reduces metal oxide into simple substance, and then the metal simple substance catalyzes carbon to generate graphene.
As still another preferred aspect, the precursor mixture further includes a binder selected from one of PVA, a carbon source (glucose, sucrose, etc.). If PVA is used as binder in this step, the carbon source may or may not be added, since the binder PVA is also a carbon source.
Still more preferably, in the aforementioned step S5, an acid solution is used as a template removing agent, and hydrogen is generated by the reaction.
The invention also discloses application of the porous graphene film obtained by the preparation method, and the porous graphene film can be applied to electrode materials or water treatment and has good market prospect.
The invention has the advantages that:
(1) In the preparation method of the porous graphene, the method for generating the graphene in situ is novel and unique, under the high-temperature condition, the carbon precursor is carbonized firstly, then the carbon reduces the metal oxide into the metal simple substance, and then the metal simple substance catalyzes the carbon to generate the graphene;
(2) The graphene film obtained by the preparation method has better conductivity and can be applied to electrode materials;
(3) In the high-temperature carbonization process, part of carbon atoms volatilize in a gaseous state during carbonization, the carbon atoms form graphene under the catalysis of a template agent, and the carbon atoms volatilized in the gaseous state endow a product with a microscopically open three-dimensional network-shaped porous structure, so that the graphene film has a good application prospect in application fields such as water treatment.
Drawings
FIG. 1 is an SEM image (2 μm) of a porous graphene film obtained by the production method of the present invention;
FIG. 2 is an SEM image (20 nm) of a porous graphene film obtained by the production method of the present invention.
Detailed Description
The invention is described in detail below with reference to the drawings and the specific embodiments.
In the invention, all raw materials are commercially available unless specified.
Example 1
The graphene film obtained in this embodiment is a graphene film having a three-dimensional pore structure inside, and the preparation steps thereof are as follows:
s1, preparing a precursor mixture
Uniformly mixing ferric oxide, mesophase pitch and water to prepare a precursor mixture, wherein the weight ratio of the ferric oxide to the mesophase pitch to the water is 3:3:10.
S2, forming a mixture film layer prepared in the step S1 on the substrate, wherein a uniform coating can be prepared by a tape casting method or a coating method, and the thickness is adjustable;
s3, drying to remove the solvent in the mixture to form an embryo membrane, wherein the drying temperature is less than 50 ℃, and the embryo membrane is preferably naturally dried;
s4, catalyzing carbon in the carbon precursor in situ to generate graphene;
the method is characterized in that graphene is generated in situ by a heat treatment method, wherein the heat treatment temperature is 600-1000 ℃ and the heat treatment time is 1-24 hours; specifically, in this example, the heat treatment temperature was 800℃and the heat treatment time was 20 hours. It should be noted that this step should be performed in a protective atmosphere, such as nitrogen, helium, argon or a mixture thereof.
And S5, taking acetic acid solution as a template removing agent, removing the template and drying to obtain the porous graphene film.
Through detection, the film thickness of the graphene film in the embodiment 1 is 100 μm, SEM images of the graphene film are shown in fig. 1 and 2, and the graphene film is clearly shown in the images to have a rich three-dimensional porous structure, wherein holes are micro-nano-sized, and the conductivity is good.
Example 2
The preparation method of this example is similar to example 1, with the main differences that the raw materials, the specific preparation steps, are as follows:
s1, preparing a precursor mixture
And (3) uniformly mixing nickel oxide, mesophase pitch and acetone to obtain a precursor mixture, wherein the weight ratio of the nickel oxide to the mesophase pitch to the acetone is 4:3:8.
S2, forming a mixture film layer prepared in the step S1 on the substrate;
s3, naturally airing to remove the solvent in the mixture to form an embryo membrane;
s4, in a protective atmosphere, heating the embryonic membrane to 600 ℃ and preserving heat for 10 hours, then heating to 900 ℃ and preserving heat for 10 hours, and carrying out in-situ catalysis on carbon in the carbon precursor to generate graphene;
and S5, taking acetic acid solution as a template removing agent, removing the template and drying to obtain the porous graphene film.
Through detection, the film thickness of the graphene film of the embodiment is 80 mu m, the graphene film has a rich three-dimensional porous structure, holes in the graphene film are micro-nano-sized, and the conductivity is good.
Example 3
The preparation method of this example is similar to example 2, with the main difference that different templates are used, and the specific preparation steps are as follows:
s1, preparing a precursor mixture
Uniformly mixing ferric chloride, ammonia water, mesophase pitch and acetone to prepare a precursor mixture, wherein the weight ratio of the ferric chloride to the ammonia water to the mesophase pitch to the acetone is 3:3:3:10.
S2, forming a mixture film layer prepared in the step S1 on the substrate by a spin coating method;
s3, naturally airing to remove the solvent in the mixture to form an embryo membrane;
s4, in a protective atmosphere, heating the embryonic membrane to 1000 ℃, preserving heat for 15 hours, and carrying out in-situ catalysis on carbon in the carbon precursor to generate graphene;
and S5, taking acetic acid solution as a template removing agent, removing the template and drying to obtain the porous graphene film.
Through detection, the film thickness of the graphene film of the embodiment is 100 mu m, the graphene film has a rich three-dimensional porous structure, holes in the graphene film are micro-nano-sized, and the conductivity is good.
Example 4
The preparation method of this example is similar to example 2, except that the precursor mixture further contains a binder, and the preparation steps are as follows:
s1, preparing a precursor mixture
Uniformly mixing ferric oxide, mesophase pitch, PVA (polyvinyl alcohol) and water to prepare a precursor mixture, wherein the weight ratio of the ferric oxide to the mesophase pitch to the PVA to the water is 3:3:20.
S2, forming a mixture film layer prepared in the step S1 on a substrate by a tape casting method;
s3, drying in a baking oven at 30 ℃ to remove the solvent in the mixture, so as to form an embryo membrane;
s4, in a protective atmosphere, catalyzing carbon in the carbon precursor in situ to generate graphene through a heat treatment process;
in this example, the heat treatment temperature was 600℃and the heat treatment time was 24 hours.
And S5, taking acetic acid solution as a template removing agent, removing the template and drying to obtain the porous graphene film.
Through detection, the film thickness of the graphene film of the embodiment is 200 mu m, the graphene film has a rich three-dimensional porous structure, holes in the graphene film are micro-nano-sized, and the conductivity is good.
In summary, in the preparation method of the porous graphene, the method for generating graphene in situ is novel and unique, under the high-temperature condition, the carbon precursor is carbonized first, then the carbon is used for reducing the metal oxide into simple substance, and then the catalytic carbon is changed into graphene. The graphene film has good conductivity, can be applied to electrode materials, has a three-dimensional network-shaped porous structure inside, and has good application prospect in the field of water treatment.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be appreciated by persons skilled in the art that the above embodiments are not intended to limit the invention in any way, and that all technical solutions obtained by means of equivalent substitutions or equivalent transformations fall within the scope of the invention.
Claims (7)
1. The preparation method of the porous graphene film is characterized by comprising the following steps of:
s1, preparing a precursor mixture: uniformly mixing a template agent, a carbon precursor and a solvent to prepare a precursor mixture; the template agent is selected from one of ferric oxide, ferroferric oxide, nickel oxide and cobalt oxide;
s2, forming a mixture film layer prepared in the step S1 on the substrate;
s3, removing the solvent in the mixture to form an embryo membrane;
s4, catalyzing carbon in the carbon precursor to generate graphene through high-temperature heat treatment, wherein the specific process is as follows: firstly carbonizing a carbon precursor, reducing a metal oxide into a metal simple substance by carbon, and catalyzing the carbon by the metal simple substance to generate graphene; the heat treatment temperature is 600-1000 ℃, and the heat treatment time is 1-24 hours;
s5, removing the template to obtain the porous graphene film.
2. The method for preparing a porous graphene film according to claim 1, wherein the carbon precursor is a substance capable of generating carbon, and is selected from one or more of pitch, carbohydrate, and alcohol.
3. The method for producing a porous graphene film according to claim 1, wherein the heat treatment is performed in a protective atmosphere of nitrogen, helium, argon or a mixed gas thereof.
4. The method for preparing the porous graphene film according to claim 1, wherein the template agent is ferric chloride and ammonia water, ferric hydroxide is generated in situ through chemical reaction, ferric oxide is generated through subsequent pyrolysis, the ferric oxide is reduced to a metal simple substance by carbon, and the carbon is catalyzed to generate graphene.
5. The method for preparing a porous graphene film according to any one of claims 1 to 4, wherein the precursor mixture further comprises a binder, and the binder is selected from one of PVA, glucose, and sucrose.
6. The method according to claim 5, wherein in the step S5, an acid solution is used as a template remover.
7. The porous graphene film obtained by the preparation method of claim 1, and application of the porous graphene film in electrode materials or water treatment.
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| CN103384001B (en) * | 2013-07-17 | 2015-09-09 | 苏州大学 | A kind of graphene combination electrode material and solid catalysis preparation method thereof |
| CN106238080B (en) * | 2016-07-08 | 2019-02-22 | 中国石油大学(北京) | The method of p-doped porous graphene and preparation method thereof and catalysis benzylamine oxidation |
| CN107301922B (en) * | 2017-06-07 | 2019-06-25 | 中国人民解放军国防科学技术大学 | Three-dimensional porous graphene nano material and its preparation method and application |
| CN107381544A (en) * | 2017-06-16 | 2017-11-24 | 中国科学院福建物质结构研究所 | A kind of graphene film and its preparation method and application |
| CN108530073B (en) * | 2017-10-08 | 2020-06-19 | 北京化工大学 | Preparation method of flexible self-supporting three-dimensional porous graphene membrane |
| CN108328605B (en) * | 2018-01-23 | 2020-04-14 | 长兴德烯科技有限公司 | High-temperature-resistant graphene heat dissipation film and preparation method thereof |
| CN108455582A (en) * | 2018-04-17 | 2018-08-28 | 福州大学 | A kind of preparation method of the three-dimensional porous grapheme material of low cost |
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| CN104701546A (en) * | 2013-12-06 | 2015-06-10 | 北京化工大学 | Porous graphene nanosheet, preparation method and application of porous graphene nanosheet as electrode material |
| CN104591176A (en) * | 2015-02-04 | 2015-05-06 | 中国科学院宁波材料技术与工程研究所 | Method for preparing graphene |
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| CN105329883A (en) * | 2015-10-14 | 2016-02-17 | 南京邮电大学 | Porous graphene preparation method |
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