CN108975725A - A kind of preparation method of the derivative graphene-carbon nano tube composite porous film of bubble - Google Patents
A kind of preparation method of the derivative graphene-carbon nano tube composite porous film of bubble Download PDFInfo
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- CN108975725A CN108975725A CN201810741758.9A CN201810741758A CN108975725A CN 108975725 A CN108975725 A CN 108975725A CN 201810741758 A CN201810741758 A CN 201810741758A CN 108975725 A CN108975725 A CN 108975725A
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- porous film
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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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
- C01B32/158—Carbon nanotubes
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The invention belongs to carbon nanomaterial preparation fields, are related to the preparation of graphene-carbon nano tube composite porous film more particularly to a kind of preparation method of the derivative graphene-carbon nano tube composite porous film of bubble.This method includes that surfactant is added to the water to the preparation for carrying out bubble aggregate template；Graphene oxide and carbon nanotube mixed solution are added in bubble aggregate template, uniform graphene oxide/carbon nanotube foam aggregate is stirred to get；By scraper plate uniform mixture is subjected to blade coating film in substrate, takes off to obtain graphene oxide-carbon nanotube composite porous film from substrate after freeze-drying；Film is heat-treated in an inert atmosphere, obtains the graphene-carbon nano tube composite porous film of independent self-supporting.The graphene-carbon nano tube composite porous film size and aperture size of invention preparation are controllable, and equipment operation is simple, and preparation cost is low, can be further amplified and carry out mass large scale preparation.
Description
Technical field
The invention belongs to carbon nanomaterial preparation fields, are related to the preparation of graphene-carbon nano tube composite porous film, especially
It is related to a kind of preparation method of derivative graphene-carbon nano tube composite porous film of bubble.
Background technique
Graphene and carbon nanotube are typical two peacekeepings one-dimensional carbon nano material respectively, have lightweight, large specific surface area,
The excellent properties such as the excellent, electric-conductivity heat-conductivity high of mechanical property, have caused the broad interest of researcher since being found.In order to will be micro-
The carbon nanomaterial of sight is applied to reality, needs to assemble them into for macroscopic body.Assemble the composite wood of graphene and carbon nanotube
Material can have both the contiguous network structure of carbon nanotube and the two-dimentional multi-layer sheet structure of graphene, and the two mutually cooperates with, formation it is more
Hole membrane structure is with important application prospects in fields such as sewage treatment, sensor, electrochemistry.
Currently, to obtain graphene-carbon nano tube composite porous film, it generally need to be mixed by chemical vapour deposition technique, solution
Legal or two methods combine.For example, Chinese patent " a kind of flexibility pulse transducer and preparation method thereof "
(CN106667451A) a kind of preparation method of carbon nanotube-graphene composite film is disclosed in.Chemical vapor deposition will be passed through
The carbon nano-tube film of area method preparation is transferred on copper-based bottom, is regenerated on the copper-based bottom by chemical vapour deposition technique later
Long one layer of graphene, forms laminated film.Chinese patent " preparation method of the pure carbon compound film of graphene-carbon nano tube "
(CN106276870A) graphene film is first grown in copper foil substrate, carbon nano tube dispersion liquid is then dispersed in graphite
Alkene film surface, and handle to obtain laminated film by electron beam irradiation.Chinese patent " graphene/carbon nano-tube nano-stack
Laminated film and preparation method thereof " (CN106995214A) is fished for the film that carbon nano pipe array pulls out in water surface formation
Graphene extra-thin film；It is slow by chemical vapour deposition technique film forming speed, it is at high cost, it is difficult to industrialize.A kind of Chinese patent " graphite
Alkene/carbon nano-tube coextruded film preparation method and applications " (CN103456520A) and Chinese patent " carbon nanotube/graphite
Alkene laminated film and preparation method thereof " (CN105236392A) first prepares mixing suspension, is film-made by filtering, in conjunction with rear
Processing obtains laminated film.However, graphene and carbon nanotube disordered arrangements in these existing composite membranes, can not achieve device to hole shape
The Effective Regulation of shape and pore size etc..
Summary of the invention
The purpose of the present invention is being directed to the deficiency of current technology of preparing, a kind of simple, efficient, controllable graphene-is provided
The compound porous membrane preparation method of carbon nanotube.
The present invention provides a kind of preparation method of derivative graphene-carbon nano tube composite porous film of bubble, including following step
It is rapid:
(1) surfactant is added in deionized water, stirring generates bubble, takes surface layer bubble aggregate；
(2) graphene oxide and carbon nanotube mixed solution are added in bubble aggregate, stirring is uniformly aoxidized
Graphene/carbon nano-tube foam aggregate；
(3) homogeneous mixture is scratched in substrate by scraper plate by film, is freeze-dried, is taken off, obtain oxidation stone
Black alkene-carbon nanotube composite porous film；
(4) then film is heat-treated in an inert atmosphere, the graphene-carbon nano tube for obtaining independent self-supporting is compound
Perforated membrane.
Surfactant is nonionic surface active agent or anionic surfactant, surface in the step (1)
Active agent content is 0.1%~10%, and single isolated bubbles diameter is 50~500 μm.
The concentration of graphene oxide solution is 5~20mg/mL in the step (2), and the concentration of carbon nano-tube solution is 0.1
~5mg/mL.
The volume ratio of the mixed solution of graphene oxide/carbon nanotube and bubble aggregate is 0.1 in the step (2)
~10:1.
Scraper plate is 100~2000 μm at a distance from substrate in the step (3), and substrate is rigid basement or flexible substrates.
Cryogenic temperature is -196~0 DEG C in the step (3).
Thermal reduction temperature is 200~1000 DEG C in the step (4), and the time is 0.5~2h.
Foam stabilizer is added in surfactant and deionized water.
When scratching film in substrate, hydrophilic treated is carried out to substrate surface first.
The preparation method of the derivative graphene-carbon nano tube composite porous film of bubble of the invention has the advantages that
1) product can be regulated and controled by adjusting the mixed solution of bubble size, graphene oxide and carbon nanotube and the volume ratio of bubble
Pore size and porosity in film；2) impurity that hydrogen bubble template introduces is few, and heat treatment can be achieved at the same time graphene oxide
The removal of reduction and surfactant；3) by the concentration and mixed proportion of control material solution, the flowing of mixture can be made
Property be suitable for knife coating be film-made.Knife coating can continuously regulate and control the parameters such as the thickness and width of membrane material, have easy to operate, work
Sequence is short, thickness is easy to control, can continuous production the advantages that, be expected to realize membrane material large area mass controllable preparation.
Detailed description of the invention
Fig. 1 is graphene oxide-carbon nanotube foam aggregate preparation flow schematic diagram；
Fig. 2 is the preparation flow schematic diagram of graphene-carbon nano tube perforated membrane.
Specific embodiment
Illustrate embodiments of the present invention below by way of particular specific embodiment, it is necessary to be pointed out that the present embodiment only
For the invention to be further described, it should not be understood as limiting the scope of the invention, which is skilled in technique
Personnel's content according to the present invention makes some nonessential modifications and adaptations, all belongs to the scope of protection of the present invention.
Since graphene oxide is electronegative materials, the type of surfactant is preferably non-ionic or anion
Type.It may be disappeared since electrostatic neutralization generates using the cationic surface active agent bubble aggregate of foam stability difference
Bubble, foam stabilizer, which is added, can weaken defoaming possibility.
Preferably, optimum efficiency graphene oxide and the mixed solution of carbon nanotube being added in bubble aggregate is both
Reunite and without obvious without obvious layering.
Preferably, hydrophily processing is carried out to scraper plate substrate to be conducive to promote painting film uniformity.
Embodiment 1
(1) 2g nonionic surface active agent F127 (PEO99-PPO65-PEO99) is added in 100mL deionized water,
Stirring takes upper foam 10mL after standing 5min；
(2) by 10mL concentration be 5mg/mL graphene oxide solution and 5mL concentration be 1mg/mL carbon nano-tube solution
Mixing is added in foam aggregate, is sufficiently stirred, obtains uniform graphene oxide/carbon nanotube bubble aggregate；
(3) select glass plate as substrate, the spacing adjusted between scraper plate and substrate is 1000 μm of progress films, by hygrometric state
Film and substrate are freezed at -80 DEG C together, and ice is distilled, and membrane material is taken off, and it is compound to obtain graphene oxide-carbon nanotube
Perforated membrane；
(4) by graphene oxide-carbon nanotube composite porous film 900 DEG C of annealing 1h in an ar atmosphere, graphene-carbon is obtained
Nanotube composite porous film.
Embodiment 2
(1) 2g anionic surfactant so lauryl sulfate (SDS) and 1g polyvinyl alcohol (PVA) are added
In 100mL deionized water, stirring takes 10mL upper foam after standing 5min；
(2) by 10mL concentration be 10mg/mL graphene oxide solution and 10mL concentration be 0.1mg/mL carbon nanotube
Solution mixing, is added in foam aggregate, is sufficiently stirred, and obtains uniform graphene oxide/carbon nanotube bubble and reunites
Body；
(3) flexible polymer PET film is subjected to plasma etched surfaces hydrophilic treated, the flexible substrates as film.
The spacing adjusted between scraper plate and substrate is 1500 μm of progress films, and hygrometric state film and substrate are freezed at -40 DEG C together,
Ice is distilled, takes membrane material off, obtains graphene oxide-carbon nanotube composite porous film；
(4) by graphene oxide-carbon nanotube composite porous film 600 DEG C of annealing 1h in an ar atmosphere, graphene-carbon is obtained
Nanotube composite porous film.
The preferred embodiment of the present invention has been described in detail above, rather than limits the invention.Of the invention
In range of the technology design, a variety of simple variants carried out to technical solution of the present invention are all belonged to the scope of protection of the present invention.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (9)
1. a kind of preparation method of the derivative graphene-carbon nano tube composite porous film of bubble, which is characterized in that this method comprises:
(1) surfactant is added in deionized water, stirring generates bubble, takes surface layer bubble aggregate；
(2) graphene oxide and carbon nanotube mixed solution are added in bubble aggregate, stirring obtains uniform graphite oxide
Alkene/carbon nanotube foam aggregate；
(3) homogeneous mixture is scratched in substrate by scraper plate by film, is freeze-dried, is taken off, obtains graphene oxide-
Carbon nanotube composite porous film；
(4) then film is heat-treated in an inert atmosphere, the graphene-carbon nano tube for obtaining independent self-supporting is compound porous
Film.
2. a kind of preparation method of the derivative graphene-carbon nano tube composite porous film of bubble as described in claim 1, feature
It is, surfactant is nonionic surface active agent or anionic surfactant, surface-active in the step (1)
Agent content is 0.1%~10%, and single isolated bubbles diameter is 50~500 μm.
3. a kind of preparation method of the derivative graphene-carbon nano tube composite porous film of bubble as described in claim 1, feature
It is, the concentration of graphene oxide solution is 5~20mg/mL in the step (2), the concentration of carbon nano-tube solution is 0.1~
5mg/mL。
4. a kind of preparation method of the derivative graphene-carbon nano tube composite porous film of bubble as described in claim 1, feature
Be, in the step (2) volume ratio of the mixed solution of graphene oxide/carbon nanotube and bubble aggregate be 0.1~
10:1。
5. a kind of preparation method of the derivative graphene-carbon nano tube composite porous film of bubble as described in claim 1, feature
It is, scraper plate is 100~2000 μm at a distance from substrate in the step (3), and substrate is rigid basement or flexible substrates.
6. a kind of preparation method of the derivative graphene-carbon nano tube composite porous film of bubble as described in claim 1, feature
It is, cryogenic temperature is -196~0 DEG C in the step (3).
7. a kind of preparation method of the derivative graphene-carbon nano tube composite porous film of bubble as described in claim 1, feature
It is, thermal reduction temperature is 200~1000 DEG C in the step (4), and the time is 0.5~2h.
8. a kind of preparation method of the derivative graphene-carbon nano tube composite porous film of bubble as described in claim 1, feature
It is, foam stabilizer is added in surfactant and deionized water.
9. a kind of preparation method of the derivative graphene-carbon nano tube composite porous film of bubble as described in claim 1, feature
It is, when scratching film in substrate, hydrophilic treated is carried out to substrate surface first.
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Cited By (4)
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| CN109631744A (en) * | 2018-12-27 | 2019-04-16 | 温州生物材料与工程研究所 | A kind of preparation method and applications of the hypersensor of polyaniline and graphene composite material based on paper substrates |
| CN111899990A (en) * | 2020-08-07 | 2020-11-06 | 北京化工大学 | Large-area continuous flexible self-supporting electrode and preparation method and application thereof |
| CN112619419A (en) * | 2020-10-23 | 2021-04-09 | 深圳前海石墨烯产业有限公司 | Composite carbon material film, composite carbon material nanofiltration membrane and preparation method |
| CN113200534A (en) * | 2021-05-19 | 2021-08-03 | 重庆交通大学 | Preparation method of graphene oxide reduction self-assembly film based on planar base film |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109631744A (en) * | 2018-12-27 | 2019-04-16 | 温州生物材料与工程研究所 | A kind of preparation method and applications of the hypersensor of polyaniline and graphene composite material based on paper substrates |
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| CN111899990B (en) * | 2020-08-07 | 2021-09-28 | 北京化工大学 | Large-area continuous flexible self-supporting electrode and preparation method and application thereof |
| CN112619419A (en) * | 2020-10-23 | 2021-04-09 | 深圳前海石墨烯产业有限公司 | Composite carbon material film, composite carbon material nanofiltration membrane and preparation method |
| CN113200534A (en) * | 2021-05-19 | 2021-08-03 | 重庆交通大学 | Preparation method of graphene oxide reduction self-assembly film based on planar base film |
| CN113200534B (en) * | 2021-05-19 | 2022-09-02 | 重庆交通大学 | Preparation method of graphene oxide reduction self-assembly film based on planar base film |
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Application publication date: 20181211 |