CN104451828A - Method for preparing vertically aligned graphene oxide film - Google Patents
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- CN104451828A CN104451828A CN201410650520.7A CN201410650520A CN104451828A CN 104451828 A CN104451828 A CN 104451828A CN 201410650520 A CN201410650520 A CN 201410650520A CN 104451828 A CN104451828 A CN 104451828A
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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, 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 materials and structures, be specifically related to a kind of method preparing vertical orientated graphene oxide film.
Background technology
Graphene has been found to be a kind of type material having application prospect.Its excellent physicochemical property likely bring the change of multiple industry.The most important variant of one as grapheme material, graphene oxide has been found prior to grapheme material and has studied.In recent years, the upsurge being relevant to Graphene research has also promoted the research of character to graphene oxide and application further.Nearest research shows, graphene oxide is actually a kind of graphene film containing multiple functional group.Graphene oxide prepared by general method, its number of plies can be individual layer or few Rotating fields, and the size of lamella is several microns or hundreds of nanometer.Edge or the inside of lamella are distributed with hydroxyl, the structure such as carboxyl or carbonyl.Can know, except carbon, in fact containing aerobic and protium in graphene oxide.Wherein the content of oxygen is only second to carbon, and this is also that it is referred to as the reason of graphene oxide composite material.
Nearest discovery shows, graphene oxide has the characteristic of multiple excellence.Different fields may be applied to.Such as, be different from the grapheme material of high conductivity, graphene oxide is excellent electrical insulator, can use as a kind of dielectric medium.Graphene oxide has the character being similar to liquid crystal when disperseing in multiple solution, have optically-active characteristic, and its laminated structure can turn to and reset under the effect of external electric field.Graphene oxide film is found to have special filtering feature especially, and it through aqueous vapor, but can present not saturating characteristic to other gases.Other gases only when aqueous vapor coexists just likely through graphene film.Deep research shows, this derives from the rapid diffusion characteristic of water molecules in the middle of graphene sheet layer, and this rapid diffusion is almost only set up water molecules.This characteristic has also edified people and has used graphene oxide film to carry out the research that sea water filter manufactures fresh water.
There is multiple method for the preparation of graphene oxide film material at present.Such as, spray-drying process, uses spraying to be sprayed on body surface by graphene oxide dispersion, makes its drying and forming-film afterwards; Natural seasoning, place in a reservoir by graphene oxide dispersion, environment container being placed in air seasoning makes its seasoning; Namely L B film method, also use L B film technology to draw film; Spin-coating method, is spin-coated on substrate surface by graphene oxide dispersion and makes its film forming.These methods all use solution for presoma, and its ultimate principle makes solvent evaporation drying film forming after precursor solution is prepared in substrate surface.In the film using this method to prepare, graphene film Rotating fields is parallel with substrate surface, and in fact the surface of film is rendered as the plane with cavity.It is pore space structure between the graphene sheet layer of most surface.So the empty area occupied on graphene film surface can much smaller than the surface-area of film.This structure is unfavorable for the diffusion of water molecules and passes graphene film.Obtain excellent filtering feature, need graphene sheet layer to have orientation perpendicular to film surface, greatly can increase the useful area of film surface in this case.In addition, after obtaining the graphene oxide structure of this structure, use the method for chemical reduction can prepare not containing the graphene film of aerobic functional group.This graphene film also has other excellent purposes.
In order to prepare this vertical orientated graphene oxide structure, current a few studies group is studied, such as, the people such as the Yeoheung Yoon of Korea S cut along the direction perpendicular to former film surface after being enclosed by parallel-oriented graphene oxide film again, are prepared into vertical orientated graphene oxide structure.This structure is comparatively tight, but there is obviously larger gap at each interlayer of the film rolled.Well imagine, may also waste more thin-film material in cutting process, so its productive rate may be restricted.The people such as Yu Zhang of Zhongshan University of the China graphene film of vertical orientated growth that used the mode of physical vapor deposition to prepare.Film has significantly vertical orientated, but has very large gap between graphene sheet layer, and film layer structure is not too tight, may limit the purposes of its related fields.Can see, in order to prepare vertical orientated Graphene or graphene oxide structure name researchist has attempted some diverse ways, but preparation-obtained membrane structure still requires further improvement.
Summary of the invention
For above technical problem, the present invention proposes to use high-voltage electric field to align the graphene oxide sheet of Solution Dispersion, and the method extracted in conjunction with solvent prepares vertical orientated graphene oxide structure.Utilize the liquid crystal characteristic of graphene oxide, making it according to the arrangement of external electric field direction, when keeping external electric field by removal of solvents, obtaining vertical orientated graphene oxide structure.
Technical scheme of the present invention is: a kind of method preparing vertical orientated graphene oxide film, and concrete steps are as follows:
(1) graphene oxide dispersion is configured;
(2) choose two pieces of insulated electro pole plates, parallel placement, back prepares conductive electrode, and conductive electrode wire connects external voltage;
(3) between the insulated electro pole plate described in step (2), inject graphene oxide dispersion, leave standstill, the infiltration battery lead plate inwall making solution intact; Open external voltage subsequently, control the field intensity that described voltage produces between two pieces of insulated electro pole plates and be less than the breaking down field strength of medium and be greater than the minimum field strength that graphene oxide can be made to produce orientation; Carry out being redirected of graphene oxide sheet in graphene oxide dispersion, complete the orientation of graphene oxide lamella;
(4) carrying out solution evaporation when keeping external voltage to open, making graphene oxide drying and forming-film;
(5) take off battery lead plate, obtain the vertical orientated graphene oxide film of self-supporting.
Further, the solvent of described graphene oxide dispersion is the one or more kinds of combinations in water, ethanol, benzene, toluene, hexanaphthene, dimethyl sulfoxide (DMSO), cyclopentanone, pimelinketone, chloroform.Adopt the dispersion graphene oxide that above-mentioned solvent can be good, more stable graphene oxide dispersion can be obtained.
Further, in step (4), graphene oxide drying and forming-film adopts lyophilize, vacuum-drying or heat drying.Do not destroy the graphene oxide chip architecture that under electric field, orientation is good.
Further, one in described two insulated electro pole plates is the substrate need preparing graphene oxide film, after Graphene drying and forming-film to be oxidized, takes off the electrode pad of non-substrate, obtains the vertical orientated graphene oxide film on substrate.
Beneficial effect of the present invention:
Use present method can obtain the higher vertical orientated graphene oxide film of quality.The present invention compared with prior art, has the following advantages:
1, major advantage of the present invention is: adopt high-voltage electric field to align the graphene oxide sheet of Solution Dispersion, the method extracted in conjunction with solvent prepares vertical orientated graphene oxide structure.Utilize the liquid crystal characteristic of graphene oxide, making it according to the arrangement of external electric field direction, when keeping external electric field by removal of solvents, obtaining vertical orientated graphene oxide structure.
2, present method can big area be prepared;
3, present method can directly be prepared on substrate;
4, present method is more flexible.The thickness of film, simply can be regulated by the distance of two-plate.The density of film can by the concentration adjustment of graphene oxide dispersion; The size that in film, the orientation degree of graphene oxide lamella can pass through applied voltage regulates;
5, present method cost is lower, and added high pressure only provides electric field, and its electric current can be ignored, so energy consumption is low.Two-plate used in the present invention can be reused;
6, use present method can prepare the film of self-supporting, film can take off for required application scenario.
Accompanying drawing explanation
Fig. 1: two-plate therebetween has the structure of graphene oxide dispersion.Wherein 1,5 electrodes being respectively bottom crown; 2,4 are respectively bottom crown, and 3 for being clipped in the graphene oxide dispersion in the middle of pole plate;
Fig. 2: the situation of to carry out orientation for applying external electric field rear oxidation graphene sheet layer with external electric field.Wherein 6 by the coupling end of applying external electric field, 7 is the graphene oxide laminated structure producing orientation after applying external electric field;
Fig. 3: be the vertical orientated graphene oxide film structure will stayed after solvent evaporates.The wherein dried vertical orientated graphene oxide film of 8 instruction;
Fig. 4: the vertical orientated graphene oxide film of the self-supporting structure after power-on and power-off pole plate is separated;
Fig. 5: vertical orientated graphene oxide film is directly prepared in the structure that substrate is formed.
Embodiment
Below in conjunction with embodiment and Figure of description, the technical scheme to invention is described in detail.
Embodiment 1:
1. use two panels thickness is the sheet glass of 500 microns, and sheet glass is of a size of 5 centimetres * 5 centimetres.The method of d.c. sputtering is used to prepare aluminium membrane electrode in the one side of sheet glass, aluminium film thickness 1 micron.Wherein, conductive electrode be prepared as conventional means, meet electroconductibility and withstand voltage, sheet glass size can regulate according to real needs, can realize big area preparation.
2. two-system is had the face-to-face parallel placement of sheet glass of electrode, outwardly, the spacing controlled between power-on and power-off pole plate is 10 microns to aluminium electrode films.As shown in Figure 1.Wherein, the thickness of film, according to real needs, simply can be regulated by the distance of two-plate.
3. working concentration is the graphene oxide water solution of 0.2mg/ml, utilizes wicking action graphene oxide water solution to be sucked between two battery lead plates, leaves standstill 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.Wherein, the density of film can by the concentration adjustment of graphene oxide dispersion, and the concentration of the graphene oxide water solution generally chosen is in 0.1-100 mg/ml; According to the difference of concentration, and prepare the difference of the conditions such as environment, time of repose can change to some extent, generally in 1-10 minute, ensures good the contacting with power-on and power-off pole plate of graphene oxide water solution.
4. aluminium membrane electrode and external high pressure are connected, voltage source is set as 2 kilovolts, and the orientation of graphene oxide is carried out in turn-on voltage source, 2 minutes orientation time.Wherein, the size that in film, the orientation degree of graphene oxide lamella can pass through applied voltage regulates, and need control the field intensity that this voltage produces between insulcrete and be less than the breaking down field strength of medium and be greater than the minimum field strength that graphene oxide can be made to produce orientation when applying this voltage.Generally speaking, this field intensity is greater than 0.2 volt/micron.The orientation time then changes, generally in the orientation completing graphene oxide lamella after 1-20 minute to some extent according to the change such as voltage swing and strength of solution.
5. the battery lead plate accompanying orientation graphene oxide is put into freeze drying box, close chamber door, open freeze drying box, set freezing temp as-20 degrees Celsius and carry out lyophilize film forming.As shown in Figure 3.Wherein, solution evaporation drying can also use other method, such as vacuum-drying, heat drying etc.No matter be that the vertical orientated graphene oxide laminated structure that has which kind of method all should control to be formed under high electric field is not destroyed.
6. after lyophilize completes, close external high pressure, take out sample, unload power-on and power-off pole plate, obtaining thickness is 10 trifling vertical orientated graphene oxide films.As shown in Figure 4.
Be prepared in the film on substrate if necessary, then need using substrate as the pole in two-plate, take off after the drying of stone graphene oxide film and electrode pad just can.As shown in Figure 5.
And the solvent of graphene oxide dispersion can be the one or more kinds of combinations in water, ethanol, benzene, toluene, hexanaphthene, dimethyl sulfoxide (DMSO), cyclopentanone, pimelinketone, chloroform.Adopt the dispersion graphene oxide that above-mentioned solvent can be good, more stable graphene oxide dispersion can be obtained.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not think that specific embodiment of the invention is confined to these explanations.Be noted that for those skilled in the art; without departing from the inventive concept of the premise; can also make somely equivalent to substitute, modification and improvement; these improve the claims in the present invention and are equal to the technical scheme after replacing, and all should be considered as belonging to protection scope of the present invention.
Claims (4)
1. prepare a method for vertical orientated graphene oxide film, it is characterized in that: concrete steps are as follows:
(1) graphene oxide dispersion is configured;
(2) choose two pieces of insulated electro pole plates, parallel placement, back prepares conductive electrode, and conductive electrode wire connects external voltage;
(3) between the insulated electro pole plate described in step (2), inject graphene oxide dispersion, leave standstill, the infiltration battery lead plate inwall making solution intact; Open external voltage subsequently, control the field intensity that described voltage produces between two pieces of insulated electro pole plates and be less than the breaking down field strength of medium and be greater than the minimum field strength that graphene oxide can be made to produce orientation; Carry out being redirected of graphene oxide sheet in graphene oxide dispersion, complete the orientation of graphene oxide lamella;
(4) carrying out solution evaporation when keeping external voltage to open, making graphene oxide drying and forming-film;
(5) take off battery lead plate, obtain the vertical orientated graphene oxide film of self-supporting.
2. a kind of method preparing vertical orientated graphene oxide film according to claim 1, is characterized in that: the solvent of described graphene oxide dispersion is the one or more kinds of combinations in water, ethanol, benzene, toluene, hexanaphthene, dimethyl sulfoxide (DMSO), cyclopentanone, pimelinketone, chloroform.
3. a kind of method preparing vertical orientated graphene oxide film according to claim 1, is characterized in that: in step (4), graphene oxide drying and forming-film adopts lyophilize, vacuum-drying or heat drying.
4. a kind of method preparing vertical orientated graphene oxide film according to claim 1, it is characterized in that: one in described two insulated electro pole plates is the substrate need preparing graphene oxide film, after Graphene drying and forming-film to be oxidized, take off the electrode pad of non-substrate, obtain the vertical orientated graphene oxide film on substrate.
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Cited By (6)
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| CN106966386A (en) * | 2017-03-09 | 2017-07-21 | 北京理工大学 | A kind of preparation method and applications of the vertical orientated thin-film material of graphene film |
| 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 |
| CN110773003A (en) * | 2019-11-11 | 2020-02-11 | 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 |
| CN114717624A (en) * | 2022-04-08 | 2022-07-08 | 广东工业大学 | Vertically oriented graphene and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966386A (en) * | 2017-03-09 | 2017-07-21 | 北京理工大学 | A kind of preparation method and applications of the vertical orientated thin-film material of graphene film |
| 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 |
| WO2020232922A1 (en) * | 2019-05-23 | 2020-11-26 | 深圳市华星光电技术有限公司 | Preparation method for optical film, optical film and display panel |
| 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 |
| CN110773003A (en) * | 2019-11-11 | 2020-02-11 | 清华大学 | Vertical orientation graphene/nano-fiber composite membrane material and preparation method and application thereof |
| 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 |
| CN114717624A (en) * | 2022-04-08 | 2022-07-08 | 广东工业大学 | Vertically oriented graphene and preparation method and application thereof |
| 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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