CN104451828B - Method for preparing vertically aligned graphene oxide film - Google Patents
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- CN104451828B CN104451828B CN201410650520.7A CN201410650520A CN104451828B CN 104451828 B CN104451828 B CN 104451828B CN 201410650520 A CN201410650520 A CN 201410650520A CN 104451828 B CN104451828 B CN 104451828B
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- graphene oxide
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- oxide film
- vertical orientated
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Abstract
The invention provides a method for preparing a vertically aligned graphene oxide film. The method comprises the following specific steps: preparing a graphene oxide dispersion liquid, selecting two insulated electrode plates, placing in parallel, and preparing conductive electrodes on backward surfaces; connecting the conductive electrodes and external voltage by using leads; injecting the graphene oxide dispersion liquid between the electrode plates obtained in the step (2), and standing, so as to enable the solution perfectly to infiltrate the inner walls of the electrode plates; starting external voltage, controlling the field intensity which is generated by the voltage between the two insulated electrode plates to be less than the breakdown field intensity of a medium and greater than the minimal field intensity capable of enabling graphene oxide to generate alignment; carrying out reorientation on graphene oxide sheets in the graphene oxide dispersion liquid, and finishing the alignment of the graphene oxide sheets; carrying out solution volatilization under the condition that the external voltage is kept in a working station, so that the graphene oxide is dried into a film; and taking down the electrode plates, so as to obtain the self-supporting vertically aligned graphene oxide film.
Description
Technical field
The invention belongs to the technical field of sophisticated semiconductor material and structure, be specifically related to one and prepare vertical orientated graphene oxide
The method of thin film.
Background technology
Graphene has been found to be the new material of a kind of great application prospect.Its excellent physicochemical properties are likely brought
The change of multiple industries.As the most important variant of one of grapheme material, graphene oxide is prior to grapheme material quilt
Find and research.In recent years, the upsurge being relevant to Graphene research has promoted the character to graphene oxide and application the most further
Research.It has recently been demonstrated that graphene oxide is actually a kind of graphene film containing multiple functional group.Conventional method
The graphene oxide of preparation, its number of plies can be monolayer or few Rotating fields, and the size of lamella is a few micrometers or hundreds of nanometer.
The edge of lamella or inside are distributed hydroxyl, the structure such as carboxyl or carbonyl.It is recognised that except carbon, graphite oxide
Actually containing aerobic and protium in alkene.Wherein the content of oxygen is only second to carbon, and this is also that it is referred to as the former of graphene oxide composite material
Cause.
Nearest discovery shows, graphene oxide has the characteristic of multiple excellence.Different fields may be applied to.Such as,
Being different from the grapheme material of high conductivity, graphene oxide is excellent electrical insulator, can use as a kind of electrolyte.
Graphene oxide has, when disperseing in multiple solution, the character being similar to liquid crystal, has optically-active characteristic, and its lamellar structure is in dispatch from foreign news agency
Can turn to and reset under the effect of field.Graphene oxide film is found to have special filtering feature especially, and it is permissible
Through aqueous vapor, but other gases are presented impermeable characteristic.Other gases only it is possible in the case of aqueous vapor coexists
Cross graphene film.In-depth study shows, this derives from the hydrone quick diffusion property in the middle of the graphene sheet layer, and this
Plant quickly diffusion almost only hydrone to be set up.This characteristic has also edified people and has used graphene oxide film to carry out sea water mistake
Filter manufactures the research of fresh water.
There is multiple method for preparing graphene oxide film material at present.Such as, spray drying method, will graphite oxide
Alkene dispersion liquid uses spraying to be sprayed on body surface, makes its drying and forming-film afterwards；Natural seasoning, will graphene oxide dispersion
After placing in a reservoir, the environment that container is placed in aeration-drying makes its natural drying；L B film method, namely use L B film
Technology draws thin film；Spin-coating method, graphene oxide dispersion will be spin-coated on substrate surface and makes its film forming.These methods all use
Solution is presoma, its ultimate principle be precursor solution is prepared in substrate surface after make solvent evaporation drying film forming.Use this
In thin film prepared by one method, graphene film Rotating fields is parallel with substrate surface, and the surface of thin film is actually rendered as having cavity
Plane.It it is pore space structure between the graphene sheet layer of most surface.So, the empty occupied area on graphene film surface can be remote
Surface area less than thin film.This structure is unfavorable for the diffusion of hydrone and through graphene film.Obtain excellent filtration special
Property, need graphene sheet layer to have the orientation being perpendicular to film surface, the effective of film surface can be greatly increased in this case
Area.It addition, after obtaining the graphene oxide structure of this structure, use the method for electronation can prepare without aerobic official
The graphene film that can roll into a ball.This graphene film also has the purposes that other are excellent.
In order to prepare this vertical orientated graphene oxide structure, current a few studies group is studied, such as, and Korea S
Yeoheung Yoon et al. parallel-oriented graphene oxide film is enclosed after further along the side being perpendicular to former film surface
To cutting, it is prepared as vertical orientated graphene oxide structure.This structure is more tight, but at each interlayer of the thin film rolled
There is significantly greater gap.Well imagine, cutting process may also be wasted more thin-film material, so its productivity can
Can be restricted.Yu Zhang of Zhongshan University of China et al. uses the mode of physical vapor deposition to be prepared for vertical orientated growth
Graphene film.Thin film has the most vertical orientated, but has the biggest gap between graphene sheet layer, and film layer structure is not
Too tight, the purposes of its related fields may be limited.It will be seen that in order to prepare vertical orientated Graphene or oxidation stone
Ink alkene structure name research worker has attempted some different methods, but preparation-obtained membrane structure need nonetheless remain for changing further
Enter.
Summary of the invention
For above technical problem, the present invention proposes to use high voltage electric field to align the scattered graphene oxide sheet of solution, in conjunction with
The method of solvent extraction prepares vertical orientated graphene oxide structure.Utilize the liquid crystal characteristic of graphene oxide so that it is according to outward
Direction of an electric field arranges, and is removed by solvent, it is thus achieved that vertical orientated graphene oxide structure in the case of keeping external electric field.
The technical scheme is that a kind of method preparing vertical orientated graphene oxide film, specifically comprise the following steps that
(1) configuration graphene oxide dispersion；
(2) choosing two pieces of insulated electro pole plates, be placed in parallel, back prepares conductive electrode, and conductive electrode wire connects external electrical
Pressure；
(3) between the insulated electro pole plate described in step (2), inject graphene oxide dispersion, stand so that solution is intact
Infiltration battery lead plate inwall；Later on external voltage, controls the field intensity that described voltage produces between two pieces of insulated electro pole plates little
The minimum field strength that graphene oxide can be made to produce orientation it is more than in the disruptive field intensity of medium；Carry out in graphene oxide dispersion
The redirection of graphene oxide sheet, completes the orientation of graphene oxide lamella；
(4) in the case of keeping external voltage to open, solution evaporation is carried out so that graphene oxide drying and forming-film；
(5) battery lead plate is taken off, it is thus achieved that the vertical orientated graphene oxide film of self-supporting.
Further, the solvent of described graphene oxide dispersion be water, ethanol, benzene, toluene, hexamethylene, dimethyl sulfoxide,
One or more kinds of combinations in Ketocyclopentane, Ketohexamethylene, chloroform.The dispersion that above-mentioned solvent can be good is used to aoxidize stone
Ink alkene, it is possible to obtain more stable graphene oxide dispersion.
Further, in step (4), graphene oxide drying and forming-film uses lyophilization, vacuum drying or heat drying.No
Destroy the graphene oxide chip architecture being orientated under electric field.
Further, a substrate being to prepare graphene oxide film in described two insulated electro pole plates, Graphene to be oxidized
After drying and forming-film, take off the electrode pad of non-substrate, it is thus achieved that the vertical orientated graphene oxide film on substrate.
Beneficial effects of the present invention:
Use this method can obtain the vertical orientated graphene oxide film that quality is higher.The present invention compared with prior art,
Have the advantage that
1, main advantages of the present invention are: use high voltage electric field to align the scattered graphene oxide sheet of solution, in conjunction with solvent
The method of extraction prepares vertical orientated graphene oxide structure.Utilize the liquid crystal characteristic of graphene oxide so that it is according to external electric field
Direction arranges, and is removed by solvent, it is thus achieved that vertical orientated graphene oxide structure in the case of keeping external electric field.
2, this method can be prepared with large area；
3, this method can directly be prepared on substrate；
4, this method is more flexible.The thickness of thin film, simply can be regulated by the distance of two-plate.The consistency of thin film can
To be regulated by the concentration of graphene oxide dispersion；In thin film, the degree of orientation of graphene oxide lamella can pass through applied electricity
The size of pressure regulates；
5, this method cost is relatively low, and added high pressure provides only electric field, and its electric current can be ignored, so energy consumption is low.Institute of the present invention
The two-plate used can be reused；
6, using this method can prepare the thin film of self-supporting, thin film can take off for required application scenario.
Accompanying drawing explanation
Figure one: two-plate is sandwiched between the structure of graphene oxide dispersion.The wherein electrode of 1,5 upper bottom crowns；2,4
Being respectively upper bottom crown, 3 is to be clipped in the graphene oxide dispersion in the middle of pole plate；
Figure two: for applying the situation that external electric field rear oxidation graphene sheet layer carries out being orientated with external electric field.Wherein 6 by being applied dispatch from foreign news agency
Connection end, 7 be to produce the graphene oxide lamellar structure of orientation after applying external electric field；
Figure three: for the vertical orientated graphene oxide film structure stayed after solvent is volatilized.Wherein 8 instructions are dried hangs down
The graphene oxide film of straight orientation；
Figure four: the vertical orientated graphene oxide film of the self-supporting structure after power-on and power-off pole plate is separated；
Figure five: vertical orientated graphene oxide film is directly prepared the structure formed on substrate.
Detailed description of the invention
Below in conjunction with embodiment and Figure of description, the technical scheme of invention is described in detail.
Embodiment 1:
1. the sheet glass using two panels thickness to be 500 microns, sheet glass a size of 5 centimetres * 5 centimetres.Use the side of d.c. sputtering
Method prepares aluminum membrane electrode, aluminum film thickness 1 micron in the one side of sheet glass.Wherein, conductive electrode be prepared as conventional means,
Meeting electric conductivity and withstanding voltage, sheet glass size can regulate according to real needs, can realize large area and prepare.
2. the sheet glass that two-system has electrode is placed in parallel face-to-face, and aluminium electrode films outwardly, controls between power-on and power-off pole plate
Spacing is 10 microns.As shown in Figure 1.Wherein, the thickness of thin film, can be according to real needs, by the distance letter of two-plate
Single regulation.
3. concentration is the graphene oxide water solution of 0.2mg/ml, utilizes capillarity graphene oxide water solution to be sucked
Between two battery lead plates, stand 5 minutes, good the contacting with power-on and power-off pole plate of graphene aqueous solution to be oxidized.As shown in Figure 2.Its
In, the consistency of thin film can be regulated by the concentration of graphene oxide dispersion, the graphene oxide water solution typically chosen
Concentration is in 0.1-100 mg/ml；According to the difference of concentration, and preparing the difference of the conditions such as environment, time of repose can become
Change, typically in 1-10 minute, it is ensured that good the contacting with power-on and power-off pole plate of graphene oxide water solution.
4. being connected with external high pressure by aluminum membrane electrode, voltage source is set as 2 kilovolts, connects voltage source, carries out graphite oxide
The orientation of alkene, 2 minutes orientationization time.Wherein, in thin film, the degree of orientation of graphene oxide lamella can be passed through to be applied
The size of voltage regulates, and need to control field intensity that this voltage produces between the insulation board breakdown field less than medium when applying this voltage
It is more than by force the minimum field strength that graphene oxide can be made to produce orientation.It is said that in general, this field intensity is more than 0.2 volt/micron.And take
Then it is varied from according to the change such as voltage swing and solution concentration to the change time, typically after 1-20 minute, completes graphite oxide
The orientation of alkene lamella.
5. the battery lead plate accompanying orientationization graphene oxide is put into freeze drying box, closes chamber door, open freeze drying box, if
Determine cryogenic temperature and carry out lyophilization film forming for-20 degrees Celsius.As shown in Figure 3.Wherein, solution evaporation is dried and can also use
Other method, is such as vacuum dried, heat drying etc..It is no matter which kind of method having of all should controlling to be formed under high electric field
Vertical orientated graphene oxide lamellar structure is not destroyed.
6. after lyophilization completes, closing external high pressure, take out sample, unload power-on and power-off pole plate, obtaining thickness is 10 microns
Vertical orientated graphene oxide film.As shown in Figure 4.
Prepare the thin film on substrate if necessary, then need substrate as the pole in two-plate, graphene film to be oxidized
Take off after drying and electrode pad just may be used.As shown in Figure 5.
And the solvent of graphene oxide dispersion can be water, ethanol, benzene, toluene, hexamethylene, dimethyl sulfoxide, Ketocyclopentane,
One or more kinds of combinations in Ketohexamethylene, chloroform.Use the dispersion graphene oxide that above-mentioned solvent can be good, energy
Enough obtain more stable graphene oxide dispersion.
Above content is to combine concrete preferred implementation further description made for the present invention, it is impossible to think the present invention
Be embodied as be confined to these explanations.It is noted that, for those skilled in the art, not
On the premise of departing from present inventive concept, it is also possible to making some equivalent replacements, modification and improvement, these are to the claims in the present invention
Improve with equivalent after technical scheme, all should be considered as belonging to protection scope of the present invention.
Claims (4)
1. the method preparing vertical orientated graphene oxide film, it is characterised in that: specifically comprise the following steps that
(1) configuration graphene oxide dispersion；
(2) choosing two pieces of insulated electro pole plates, be placed in parallel, back prepares conductive electrode, and conductive electrode wire connects external electrical
Pressure；
(3) between the insulated electro pole plate described in step (2), inject graphene oxide dispersion, stand so that solution is intact
Infiltration battery lead plate inwall；Later on external voltage, controls the field intensity that described voltage produces between two pieces of insulated electro pole plates little
The minimum field strength that graphene oxide can be made to produce orientation it is more than in the disruptive field intensity of medium；Carry out in graphene oxide dispersion
The redirection of graphene oxide sheet, completes the orientation of graphene oxide lamella；
(4) in the case of keeping external voltage to open, solution evaporation is carried out so that graphene oxide drying and forming-film；
(5) battery lead plate is taken off, it is thus achieved that the vertical orientated graphene oxide film of self-supporting.
A kind of method preparing vertical orientated graphene oxide film the most according to claim 1, it is characterised in that: described
The solvent of graphene oxide dispersion be water, ethanol, benzene, toluene, hexamethylene, dimethyl sulfoxide, Ketocyclopentane, Ketohexamethylene,
One or more kinds of combinations in chloroform.
A kind of method preparing vertical orientated graphene oxide film the most according to claim 1, it is characterised in that: step
(4) in, graphene oxide drying and forming-film uses lyophilization, vacuum drying or heat drying.
A kind of method preparing vertical orientated graphene oxide film the most according to claim 1, it is characterised in that: described
A substrate being to prepare graphene oxide film in two pieces of insulated electro pole plates, after Graphene drying and forming-film to be oxidized, takes off
The electrode pad of non-substrate, it is thus achieved that the vertical orientated graphene oxide film on substrate.
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| CN106966386B (en) * | 2017-03-09 | 2019-06-11 | 北京理工大学 | A kind of preparation method and applications of graphene film vertical orientation thin-film material |
| CN110221363A (en) * | 2019-05-23 | 2019-09-10 | 深圳市华星光电技术有限公司 | Preparation method, optical diaphragm and the display panel of optical diaphragm |
| CN110511029A (en) * | 2019-09-10 | 2019-11-29 | 北京中石伟业科技无锡有限公司 | A kind of method that binder free graphene oxide prepares high orientation graphite block body |
| CN110773003B (en) * | 2019-11-11 | 2021-08-24 | 清华大学 | Vertical orientation graphene/nano-fiber composite membrane material and preparation method and application thereof |
| CN111825347A (en) * | 2020-07-03 | 2020-10-27 | 广东工业大学 | Device and method for orienting glass flakes by electric field |
| CN114717624B (en) * | 2022-04-08 | 2023-08-22 | 广东工业大学 | Vertically oriented graphene and preparation method and application thereof |
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| CN102021633A (en) * | 2009-09-09 | 2011-04-20 | 中国科学院金属研究所 | Preparation method of graphene thin film field emission material |
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