CN106395802A - Method for preparing graphene porous membrane - Google Patents
Method for preparing graphene porous membrane Download PDFInfo
- Publication number
- CN106395802A CN106395802A CN201610808334.0A CN201610808334A CN106395802A CN 106395802 A CN106395802 A CN 106395802A CN 201610808334 A CN201610808334 A CN 201610808334A CN 106395802 A CN106395802 A CN 106395802A
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- microsphere
- graphene
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- pore creating
- creating material
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention provides a method for preparing a graphene porous membrane. The method includes the steps that oxidized graphite is added into water, oxidized graphite dispersion liquid is obtained and subjected to ultrasonic dispersion, and an oxidized graphene solution is obtained; a pore forming agent is added into the oxidized graphene solution and evenly dispersed into oxidized graphene, the mixture is subjected to suction filtration and/or dried, and a composite membrane of the oxidized graphene and the pore forming agent is obtained; the composite membrane of the oxidized graphene and the pore forming agent is reduced and washed, and a composite membrane of graphene and the pore forming agent is obtained; the pore forming agent is removed with an organic solvent, and under the moist condition, the product is further treated with the critical point drying method, and the graphene porous membrane is obtained; the pore forming agent is one or more of homopolymer microspheres and copolymer microspheres. The size of pores inside the graphene porous membrane prepared with the method ranges from 100 nm to 1,000 nm, the porosity can be regulated and controlled by regulating the concentration or the size of the pore forming agent, the yield of the graphene porous membrane is high, and an operating device is simple.
Description
Technical field
The invention belongs to field of material technology is and in particular to a kind of preparation method of Graphene perforated membrane.
Background technology
Graphene is bi-dimensional cellular shape network, its unique atomic structure and the electronics being made up of the monoatomic layer of carbon
Structure, makes material have excellent electricity, calorifics and mechanical performance, has the theoretical specific surface area of super large simultaneously（Theoretical Calculation
It is worth for 2600m2/g）, it is the preferred of electrode material for super capacitor of new generation.But the incomplete reducing degree of Graphene and reduction
During the stacking that produced due to van der Waals interaction, cause the electric conductivity of material to be deteriorated, specific surface area is far below theoretical value,
Thus have impact on final performance.
In order to reduce the stacking of Graphene further, increase the specific surface area of solid graphite alkene, this is accomplished by from molecule chi
On degree, design effectively is carried out to its microstructure.Graphene perforated membrane remains the excellent proper property of grapheme material, simultaneously
There is higher specific surface area, can largely improve material property and fault of construction.Graphene perforated membrane can give it
New performance and application, such as electric energy conversion, storage device, electronic field emission source, thermal diffusion layer, oil phase adsorbent and catalyst carry
Body etc..
At present, the preparation of Graphene perforated membrane is mainly by way of calcining reduction.This method has apparent lacking
Point：One is that energy consumption is big, and treatment conditions are harsh；Two is the expansion that heat treatment process can cause porous membrane volume；Importantly,
All uncontrollable, the hole size heterogeneity to the number in product hole and pore size, this uncontrollable and unordered structure is unfavorable for grinding
The person of studying carefully is to the research of storage in loose structure for the material and transmission principle and understanding.And it is critical to adopt organic solvent dissolving to combine
The dry mode of point prepares the method for Graphene perforated membrane, and there is not been reported.The treatment conditions of this preparation method are simple, gentle,
Quickly, can effectively prevent sample from subtle flow occurring, obtained Graphene perforated membrane has that pore diameter range is big, controllable and
Homogeneous feature.
Content of the invention
It is an object of the invention to provide a kind of simple, method of efficiently preparing Graphene perforated membrane, can significantly improve
The specific surface area of graphene film, realizes quickly preparing in a large number, and answers in the research of material science for Graphene perforated membrane
With having a very big significance.
The present invention provides a kind of preparation method of Graphene perforated membrane, comprises the following steps：
（1）Graphite oxide is added to the water, obtains graphite oxide dispersion, ultrasonic disperse, obtain graphene oxide solution；
（2）Add pore creating material in above-mentioned graphene oxide solution, so that pore creating material is dispersed in graphene oxide, sucking filtration
And/or be dried, obtain the complexes membrane of graphene oxide and pore creating material；
（3）The complexes membrane of graphene oxide and pore creating material is reduced, washing, obtain the complex of Graphene and pore creating material
Film；
（4）Pore creating material is removed with organic solvent, in a wetted condition, processes 1-5h with critical-point drying method further, obtain stone
Black alkene perforated membrane.
Described step（1）The concentration of middle graphite oxide dispersion is 1-10mg/mL.
Described step（1）The middle ultrasonic disperse time is 0.5-5h.
Described step（2）Middle pore creating material is in homopolymer microsphere, bipolymer microsphere and multiple copolymer microsphere
Plant or multiple.
Described step（2）Middle graphene oxide is 0.05-10 with the mass ratio of pore creating material:1, preferably 0.1-2: 1.
Described step（3）The reducing agent of middle employing is hydroiodic acid, and the concentration expressed in percentage by volume of hydroiodic acid solution is 40-60%；Oxygen
Graphite alkene with the amount ratio of hydroiodic acid is（0.1-5）g:1L；Reaction temperature is 80-100 DEG C；Recovery time is 1-8h.
Described step（4）The organic solvent of middle employing is toluene, oxolane, in the mixture of oxolane and acetone
One or more.
The hole size within Graphene perforated membrane that this invention prepares is in 100-1000nm scope.
Compared with the preparation method of the Graphene perforated membrane reported before, the remarkable advantage of the present invention is：
Product hole size uniformity, can be by adjusting the size Control hole size of pore creating material, can be by adjusting pore creating material
Concentration regulates and controls porosity, is conducive to studying and understands storage in loose structure for the material and transmission principle；
Critical-point drying method removes liquid in sample under not having the critical state of gas and liquid surface, has while pore-creating
Effect prevents loose structure that subtle flow occurs, and instrumentation is simple, takes short.
The Graphene perforated membrane yield of this method preparation is affected by inventory, improves inventory, and yield can reach a gram level.
Brief description
The SEM photograph of the graphene oxide that Fig. 1 prepares for embodiment 1 and the complexes membrane of polystyrene microsphere；
The SEM photograph of the Graphene perforated membrane that Fig. 2 prepares for embodiment 1.
Specific embodiment
With specific embodiment, technical scheme is described in detail below in conjunction with the accompanying drawings.It should be understood that
It is that specific embodiment described herein is merely to illustrate and explains the present invention, is not limited to the present invention.
Embodiment 1
（1）50mg graphite oxide is added in 50mL water, obtains graphite oxide dispersion, ultrasonic disperse 1h, obtain graphite oxide
Alkene solution；
（2）Add 1g polystyrene microsphere in above-mentioned graphene oxide solution, make polystyrene microsphere be dispersed in oxidation
In Graphene, it is dried, obtains the complexes membrane of graphene oxide and polystyrene microsphere；
（3）The hydroiodic acid solution being 57% using 0.2L concentration expressed in percentage by volume is combined with polystyrene microsphere to graphene oxide
Thing film is reduced, and reaction temperature is 80 DEG C, and the recovery time is 2h, washing, obtains the compound of Graphene and polystyrene microsphere
Thing film；
（4）Polystyrene microsphere is removed with oxolane, and repeatedly replaces oxolane with dehydrated alcohol, by the sample after processing
It is stored in dehydrated alcohol, processes 2h with critical-point drying method further, obtain Graphene perforated membrane.
Embodiment 2
（1）500mg graphite oxide is added in 50mL water, obtains graphite oxide dispersion, ultrasonic disperse 5h, obtain graphite oxide
Alkene solution；
（2）Add 0.05g poly (methyl methacrylate) micro-sphere in above-mentioned graphene oxide solution, make polymethyl methacrylate
Microsphere is dispersed in graphene oxide, sucking filtration, obtains the complex of graphene oxide and poly (methyl methacrylate) micro-sphere
Film；
（3）The hydroiodic acid solution being 40% using 5L concentration expressed in percentage by volume is to graphene oxide and poly (methyl methacrylate) micro-sphere
Complexes membrane reduced, reaction temperature be 100 DEG C, the recovery time be 8h, washing, obtain Graphene and polymethylacrylic acid
The complexes membrane of methyl ester microsphere；
（4）Poly (methyl methacrylate) micro-sphere is removed with toluene, and repeatedly replaces toluene with dehydrated alcohol, by the sample after processing
It is stored in dehydrated alcohol, processes 1h with critical-point drying method further, obtain Graphene perforated membrane.
Embodiment 3
（1）200mg graphite oxide is added in 50mL water, obtains graphite oxide dispersion, ultrasonic disperse 1.5h, obtain aoxidizing stone
Black alkene solution；
（2）Add 0.1g poly- [styrene methyl methacrylate-acrylic acid] microsphere in above-mentioned graphene oxide solution, make
Poly- [styrene methyl methacrylate-acrylic acid] microsphere is dispersed in graphene oxide, is dried, obtains graphite oxide
Alkene and the complexes membrane of poly- [styrene methyl methacrylate-acrylic acid] microsphere；
（3）The hydroiodic acid solution being 47% using 0.5L concentration expressed in percentage by volume is to graphene oxide and poly- [styrene-methyl propylene
Sour methyl ester-acrylic acid] complexes membrane of microsphere reduced, and reaction temperature is 90 DEG C, and the recovery time is 4h, and washing obtains stone
Black alkene and the complexes membrane of poly- [styrene methyl methacrylate-acrylic acid] microsphere；
（4）Poly- [styrene methyl methacrylate-acrylic acid] microsphere is removed with oxolane, multiple with dehydrated alcohol first
Displacement oxolane, by the sample preservation after processing in dehydrated alcohol, processes 5h with critical-point drying method further, obtains stone
Black alkene perforated membrane.
Embodiment 4
（1）50mg graphite oxide is added in 50mL water, obtains graphite oxide dispersion, ultrasonic disperse 0.5h, obtain aoxidizing stone
Black alkene solution；
（2）Add 0.5g polystyrene microsphere in above-mentioned graphene oxide solution, make polystyrene microsphere be dispersed in oxygen
In graphite alkene, sucking filtration and drying, obtain the complexes membrane of graphene oxide and polystyrene microsphere；
（3）The hydroiodic acid solution being 60% using 0.5L concentration expressed in percentage by volume is combined with polystyrene microsphere to graphene oxide
Thing film is reduced, and reaction temperature is 80 DEG C, and the recovery time is 1h, washing, obtains the compound of Graphene and polystyrene microsphere
Thing film；
（4）Polystyrene microsphere is removed with the mixture of oxolane and acetone, and repeatedly replaces oxolane with dehydrated alcohol
With the mixture of acetone, by the sample preservation after processing in dehydrated alcohol, process 3h with critical-point drying method further, obtain
Graphene perforated membrane.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (8)
1. a kind of preparation method of Graphene perforated membrane is it is characterised in that the method includes：
（1）Graphite oxide is added to the water, obtains graphite oxide dispersion, ultrasonic disperse, obtain graphene oxide solution；
（2）Add pore creating material in above-mentioned graphene oxide solution, so that pore creating material is dispersed in graphene oxide, sucking filtration
And/or be dried, obtain the complexes membrane of graphene oxide and pore creating material；
（3）The complexes membrane of graphene oxide and pore creating material is reduced, washing, obtain the complex of Graphene and pore creating material
Film；
（4）Pore creating material is removed with organic solvent, in a wetted condition, processes 1-5h with critical-point drying method further, obtain stone
Black alkene perforated membrane.
2. method according to claim 1 it is characterised in that：Described step（1）The concentration of middle graphite oxide dispersion is
1-10mg/mL.
3. method according to claim 1 it is characterised in that：Described step（1）The middle ultrasonic disperse time is 0.5-5h.
4. method according to claim 1 it is characterised in that：Described step（2）Middle pore creating material is homopolymer microsphere, binary
One or more of copolymer microsphere and multiple copolymer microsphere.
5. method according to claim 4 it is characterised in that：
Described homopolymer microsphere is polystyrene microsphere, in poly (methyl methacrylate) micro-sphere and butyl polyacrylate microsphere
Plant or multiple；Preferably, described homopolymer microsphere be one of polystyrene microsphere and poly (methyl methacrylate) micro-sphere or
Multiple；
Described copolymer microsphere is poly- [styrene methyl methacrylate] microsphere, poly- [Styrene And Butyl-acrylate] microsphere,
Poly- [methacrylic acid-polyglycidyl] microsphere, poly- [methyl methacrylate-butyl acrylate] microsphere and poly- [styrene-methyl
One or more of methyl acrylate-acrylic acid] microsphere；Preferably, described copolymer microsphere is poly- [styrene-methyl third
E pioic acid methyl ester-acrylic acid] microsphere.
6. method according to claim 1 it is characterised in that：Described step（2）Middle graphene oxide and the matter of pore creating material
Amount ratio is 0.05-10:1, preferably 0.1-2: 1.
7. method according to claim 1 it is characterised in that：Described step（3）The reducing agent of middle employing is hydroiodic acid, hydrogen
The concentration expressed in percentage by volume of iodic acid solution is 40-60%；Graphene oxide with the amount ratio of hydroiodic acid is（0.1-5）g:1L；Reaction temperature
Spend for 80-100 DEG C；Recovery time is 1-8h.
8. method according to claim 1 it is characterised in that：Described step（4）The organic solvent of middle employing is toluene, four
One or more of mixture of hydrogen furan, oxolane and acetone.
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Cited By (5)
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| CN107376006A (en) * | 2017-07-28 | 2017-11-24 | 浙江理工大学 | A kind of preparation method of porous artificial skin receptor |
| 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 |
| 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 |
| 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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| 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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