CN106395802B - Preparation method of graphene porous membrane - Google Patents
Preparation method of graphene porous membrane Download PDFInfo
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- CN106395802B CN106395802B CN201610808334.0A CN201610808334A CN106395802B CN 106395802 B CN106395802 B CN 106395802B CN 201610808334 A CN201610808334 A CN 201610808334A CN 106395802 B CN106395802 B CN 106395802B
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Abstract
The invention provides a preparation method of a graphene porous membrane, wherein the method comprises the steps of adding graphite oxide into water to obtain a graphite oxide dispersion liquid, and performing ultrasonic dispersion to obtain a graphene oxide solution; adding a pore-forming agent into the graphene oxide solution, uniformly dispersing the pore-forming agent in the graphene oxide, and performing suction filtration and/or drying to obtain a composite film of the graphene oxide and the pore-forming agent; reducing and washing the composite film of the graphene oxide and the pore-forming agent to obtain the composite film of the graphene and the pore-forming agent; removing the pore-forming agent by using an organic solvent, and further processing by using a critical point drying method under a humid condition to obtain a graphene porous membrane; the pore-forming agent is one or more of homopolymer microspheres and copolymer microspheres. The pore size in the graphene porous membrane prepared by the method is within the range of 100-1000nm, the porosity can be regulated and controlled by adjusting the concentration or size of the pore-forming agent, the yield of the graphene porous membrane is high, and the operation equipment is simple.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of a graphene porous membrane.
Background
The graphene is a two-dimensional honeycomb grid structure formed by a single atomic layer of carbon, and the unique atomic structure and electronic structure of the graphene enable the material to have excellent electrical, thermal and mechanical properties and simultaneously have an ultra-large theoretical specific surface area (theoretical calculation value is 2600 m)2And/g) is the preferable material of the electrode of the super capacitor of the new generation. However, the final performance is affected by the degree of incomplete reduction of graphene and stacking of graphene due to van der waals force during reduction, which leads to poor conductivity of the material and a much lower specific surface area than a theoretical value.
In order to further reduce the stacking of graphene and increase the specific surface area of solid graphene, the microstructure of the solid graphene needs to be designed effectively from a molecular scale. The graphene porous membrane reserves the excellent inherent performance of the graphene material, has higher specific surface area and can improve the material performance and the structural defects to a greater extent. The graphene porous membrane can endow the graphene porous membrane with new performance and application, such as electric energy conversion, storage devices, electron field emission sources, thermal diffusion layers, oil phase adsorbents, catalyst carriers and the like.
At present, the preparation of the graphene porous membrane is mainly realized by a calcination reduction mode. This method has significant disadvantages: firstly, the energy consumption is high, and the treatment conditions are harsh; secondly, the volume of the porous membrane is expanded in the heat treatment process; more importantly, the obtained product has uncontrollable pore size and non-uniform pore size, and the uncontrollable and disordered structure is not beneficial to researchers for researching and understanding the storage and transmission principle of the substance in the porous structure. However, a method for preparing the graphene porous membrane by adopting a mode of dissolving with an organic solvent and drying at a critical point is not reported. The preparation method has the advantages of simple, mild and rapid treatment conditions, and can effectively prevent the sample from generating fine deformation, and the prepared graphene porous membrane has the characteristics of large aperture range, controllability and uniformity.
Disclosure of Invention
The invention aims to provide a simple and efficient method for preparing a graphene porous membrane, which can obviously improve the specific surface area of the graphene membrane, realize large-scale rapid preparation and has great significance for the research and application of the graphene porous membrane in the field of material science.
The invention provides a preparation method of a graphene porous membrane, which comprises the following steps:
(1) adding graphite oxide into water to obtain a graphite oxide dispersion liquid, and performing ultrasonic dispersion to obtain a graphene oxide solution;
(2) adding a pore-forming agent into the graphene oxide solution, uniformly dispersing the pore-forming agent in the graphene oxide, and performing suction filtration and/or drying to obtain a composite film of the graphene oxide and the pore-forming agent;
(3) reducing and washing the composite film of the graphene oxide and the pore-forming agent to obtain the composite film of the graphene and the pore-forming agent;
(4) removing the pore-forming agent by using an organic solvent, and further processing for 1-5h by using a critical point drying method under a wet condition to obtain the graphene porous membrane.
The concentration of the graphite oxide dispersion liquid in the step (1) is 1-10 mg/mL.
The ultrasonic dispersion time in the step (1) is 0.5-5 h.
And (3) in the step (2), the pore-forming agent is one or more of homopolymer microspheres, binary copolymer microspheres and multi-component copolymer microspheres.
The mass ratio of the graphene oxide to the pore-forming agent in the step (2) is 0.05-10: 1, preferably 0.1-2: 1.
The reducing agent adopted in the step (3) is hydroiodic acid, and the volume percentage concentration of the hydroiodic acid solution is 40-60%; the dosage ratio of the graphene oxide to the hydroiodic acid is (0.1-5) g: 1L; the reaction temperature is 80-100 ℃; the reduction time is 1-8 h.
The organic solvent adopted in the step (4) is one or more of toluene, tetrahydrofuran and a mixture of tetrahydrofuran and acetone.
The pore size in the graphene porous membrane prepared by the method is within the range of 100-1000 nm.
Compared with the preparation method of the graphene porous membrane reported previously, the preparation method has the following remarkable advantages:
the product has uniform pore size, the size of the pores can be controlled by adjusting the size of the pore-forming agent, and the porosity can be regulated by adjusting the concentration of the pore-forming agent, so that the research and the understanding of the storage and transmission principles of the substances in the porous structure are facilitated;
the critical point drying method removes liquid in a sample under the critical state without a gas and liquid interface, effectively prevents a porous structure from generating fine deformation while pore forming, and has simple instrument operation and short consumed time.
The yield of the graphene porous membrane prepared by the method is influenced by the feeding amount, the feeding amount is increased, and the yield can reach gram level.
Drawings
Fig. 1 is an SEM photograph of a composite film of graphene oxide and polystyrene microspheres prepared in example 1;
fig. 2 is an SEM photograph of the graphene porous membrane prepared in example 1.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
(1) Adding 50mg of graphite oxide into 50mL of water to obtain a graphite oxide dispersion solution, and performing ultrasonic dispersion for 1h to obtain a graphene oxide solution;
(2) adding 1g of polystyrene microspheres into the graphene oxide solution, uniformly dispersing the polystyrene microspheres in the graphene oxide, and drying to obtain a composite film of the graphene oxide and the polystyrene microspheres;
(3) reducing the graphene oxide and polystyrene microsphere composite film by using 0.2L of 57% hydriodic acid solution in volume percentage concentration, washing to obtain the graphene and polystyrene microsphere composite film, wherein the reaction temperature is 80 ℃, and the reduction time is 2 hours;
(4) removing the polystyrene microspheres by using tetrahydrofuran, replacing the tetrahydrofuran by using absolute ethyl alcohol for multiple times, storing the treated sample in the absolute ethyl alcohol, and further treating for 2 hours by using a critical point drying method to obtain the graphene porous membrane.
Example 2
(1) Adding 500mg of graphite oxide into 50mL of water to obtain a graphite oxide dispersion solution, and performing ultrasonic dispersion for 5 hours to obtain a graphene oxide solution;
(2) adding 0.05g of polymethyl methacrylate microspheres into the graphene oxide solution to uniformly disperse the polymethyl methacrylate microspheres in the graphene oxide, and performing suction filtration to obtain a composite film of the graphene oxide and the polymethyl methacrylate microspheres;
(3) reducing the composite membrane of the graphene oxide and the polymethyl methacrylate microspheres by adopting 5L of hydriodic acid solution with the volume percentage concentration of 40%, wherein the reaction temperature is 100 ℃, the reduction time is 8h, and washing to obtain the composite membrane of the graphene and the polymethyl methacrylate microspheres;
(4) removing the polymethyl methacrylate microspheres by using toluene, replacing the toluene with absolute ethyl alcohol for multiple times, storing the treated sample in the absolute ethyl alcohol, and further treating for 1h by using a critical point drying method to obtain the graphene porous membrane.
Example 3
(1) Adding 200mg of graphite oxide into 50mL of water to obtain a graphite oxide dispersion solution, and performing ultrasonic dispersion for 1.5h to obtain a graphene oxide solution;
(2) adding 0.1g of poly [ styrene-methyl methacrylate-acrylic acid ] microspheres into the graphene oxide solution, uniformly dispersing the poly [ styrene-methyl methacrylate-acrylic acid ] microspheres in the graphene oxide, and drying to obtain a composite film of the graphene oxide and the poly [ styrene-methyl methacrylate-acrylic acid ] microspheres;
(3) reducing the composite film of graphene oxide and poly [ styrene-methyl methacrylate-acrylic acid ] microspheres by adopting 0.5L of hydroiodic acid solution with the volume percentage concentration of 47%, wherein the reaction temperature is 90 ℃, the reduction time is 4h, and washing to obtain the composite film of graphene and poly [ styrene-methyl methacrylate-acrylic acid ] microspheres;
(4) removing the poly [ styrene-methyl methacrylate-acrylic acid ] microspheres by using tetrahydrofuran, firstly replacing the tetrahydrofuran by using absolute ethyl alcohol for multiple times, storing the treated sample in the absolute ethyl alcohol, and further treating for 5 hours by using a critical point drying method to obtain the graphene porous membrane.
Example 4
(1) Adding 50mg of graphite oxide into 50mL of water to obtain a graphite oxide dispersion liquid, and performing ultrasonic dispersion for 0.5h to obtain a graphene oxide solution;
(2) adding 0.5g of polystyrene microspheres into the graphene oxide solution to uniformly disperse the polystyrene microspheres in the graphene oxide, and performing suction filtration and drying to obtain a composite film of the graphene oxide and the polystyrene microspheres;
(3) reducing the composite membrane of the graphene oxide and the polystyrene microspheres by using 0.5L of 60% hydriodic acid solution with volume percentage concentration, washing to obtain the composite membrane of the graphene oxide and the polystyrene microspheres, wherein the reaction temperature is 80 ℃ and the reduction time is 1 h;
(4) and removing the polystyrene microspheres by using a mixture of tetrahydrofuran and acetone, replacing the mixture of tetrahydrofuran and acetone by using absolute ethyl alcohol for multiple times, storing the treated sample in the absolute ethyl alcohol, and further treating for 3 hours by using a critical point drying method to obtain the graphene porous membrane.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (5)
1. A preparation method of a graphene porous membrane is characterized by comprising the following steps:
(1) adding graphite oxide into water to obtain a graphite oxide dispersion liquid, and performing ultrasonic dispersion to obtain a graphene oxide solution;
(2) adding a pore-forming agent into the graphene oxide solution, uniformly dispersing the pore-forming agent in the graphene oxide, and performing suction filtration and/or drying to obtain a composite film of the graphene oxide and the pore-forming agent;
(3) reducing and washing the composite film of the graphene oxide and the pore-forming agent to obtain the composite film of the graphene and the pore-forming agent;
(4) removing the pore-forming agent by using an organic solvent, replacing the organic solvent with absolute ethyl alcohol for multiple times, storing the treated composite membrane in the absolute ethyl alcohol, and further treating for 1-5 hours by using a critical point drying method to obtain a graphene porous membrane;
wherein, the pore-forming agent in the step (2) is one or more of polystyrene microspheres and polymethyl methacrylate microspheres; the reducing agent adopted in the step (3) is hydroiodic acid, and the volume percentage concentration of the hydroiodic acid solution is 40-60%; the dosage ratio of the graphene oxide to the hydroiodic acid is (0.1-5) g: 1L; the reaction temperature is 80-100 ℃; the reduction time is 1-8 h.
2. The method of claim 1, wherein: the concentration of the graphite oxide dispersion liquid in the step (1) is 1-10 mg/mL.
3. The method of claim 1, wherein: the ultrasonic dispersion time in the step (1) is 0.5-5 h.
4. The method of claim 1, wherein: the mass ratio of the graphene oxide to the pore-forming agent in the step (2) is 0.1-2: 1.
5. The method of claim 1, wherein: the organic solvent adopted in the step (4) is one or more of toluene, tetrahydrofuran and a mixture of tetrahydrofuran and acetone.
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| CN107376006B (en) * | 2017-07-28 | 2020-08-18 | 浙江理工大学 | Preparation method of porous artificial skin receptor |
| CN107689271A (en) | 2017-08-22 | 2018-02-13 | 京东方科技集团股份有限公司 | Preparation method, porous graphene film and the electronic product of porous graphene film |
| CN107601476A (en) * | 2017-09-11 | 2018-01-19 | 长沙小新新能源科技有限公司 | A kind of preparation method of High-performance graphene perforated membrane |
| CN111547707A (en) * | 2020-04-24 | 2020-08-18 | 中国科学院山西煤炭化学研究所 | Graphene bubble film and preparation method and application thereof |
| CN114373897A (en) * | 2020-10-14 | 2022-04-19 | 山东欧铂新材料有限公司 | Porous graphene/artificial graphite composite material, preparation method thereof and lithium ion battery |
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