CN106276872A - The preparation method of self-supporting transparent conductive graphene membrane - Google Patents
The preparation method of self-supporting transparent conductive graphene membrane Download PDFInfo
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Abstract
The invention provides the preparation method of self-supporting transparent conductive graphene membrane, including: with one layer of graphene oxide A of filter membrane pull-up, obtain material I；The aqueous solution of organic amine soaks, prepares material II；With one layer of graphene oxide B of material II pull-up, obtain sandwich composite；By gained sandwich composite, with aqueous acetone solution moistening to material deliquescing, then it is completely dissolved to its filter membrane with acetone soak material, obtains material IV；Graphene oxide in reducing material IV, obtains the graphene film of self-supporting electrically conducting transparent.Present invention uses organic amine, the method removing substrate is then, first pass through moistening and play the effect of " punching ", change dicyandiamide solution again and thoroughly remove substrate, making thin film not cracky in operating process, overall step is simple, and operation is simple, the thin film prepared can be very big and thin, has high light transmission, good pliability and electric conductivity simultaneously.
Description
Technical field
The present invention relates to technical field of nano material, particularly relate to the preparation of a kind of self-supporting transparent conductive graphene membrane
Method.
Background technology
Traditional transparency electrode tin indium oxide (ITO) has met the electrode requirement to high efficiency of transmission luminous energy with conduction electric current,
There is higher light transmission rate, low square resistance, but, its cost is high, fragility is frangible, the photoelectric device of preparation is flimsy
Shortcoming, hinders the actual application of specific area.
Graphene is a kind of special material, and the hexagoinal lattice form with sp2 carbon atom hybrid orbital composition lines up
Carry out the plane layer structure in honeycomb lattice, be to have now been found that the thinnest two-dimensional material.Graphene film is as most potential
Substitute the material of conventional transparent electrode, show and actual application the such as transparency electrode of solaode can be big at flat liquid crystal
Reduce greatly production cost, also can improve the flexility of material simultaneously.
At present, it has been found that a lot of about the method preparing graphene film, such as Langmuir-Blodgett method
(being called for short LB method), the method can repeat to prepare graphene layer with instrument (also known as LB instrument) on the water surface.
" U.S.'s nanometer " (ACS Nano, 2011 7 phase of volume 5 page 6039) reports and utilizes LB method to make on the glass sheet
For having gone out graphene film, separately there is a lot of document to disclose and use LBL, the spraying method such as spin coating and vapour deposition at silicon chip, glass
The method growing graphene film on glass sheet and copper sheet.
But the substrate of these methods cannot be removed, seriously limit transferability and the process operation of thin-film material,
And the surface of these substrates has a lot of defects, cause thin-film material in uneven thickness of preparation.
Summary of the invention
For the defect of currently available technology, the invention provides the preparation of a kind of self-supporting transparent conductive graphene membrane
Method, the method can remove substrate well, and preparation method is the easiest, the graphene film mechanical performance for preparing, thoroughly
Light rate, electric conductivity are the most fine.
On the one hand, the invention provides the preparation method of self-supporting transparent conductive graphene membrane, comprise the following steps:
A. Langmuir-Blodgett method prepares graphene oxide layer on the water surface；
B. with filter membrane vertical one layer of graphene oxide A of pull-up from the water surface, the material I that filter membrane is compound with graphene oxide A is obtained,
Drying processes (preferably) or moist and carries out next-step operation, and described filter membrane is composite fibre ester microporous filter membrane (water system), i.e.
The water system microporous filter membrane that cellulose nitrate and acetate fiber are made, is preferably made (two acetic acid fibres by cellulose nitrate and diacetate fiber
The weight ratio of dimension can be 52% ~ 57%, the as above water system microporous filter membrane product of Asia, Haixing County scavenging material factory)；Filter sizes can be
400-500nm, preferably 450nm；
C., b walks resulting materials I soak in the aqueous solution of organic amine, make the surface of graphene oxide A covalently bound have organic
Amine layer, prepares the material II that filter membrane, graphene oxide and organic amine are compound, and described organic amine is macromolecule polyalcohol or little molecule
Organic substance, and each molecule is with plural amino or imino group, such as aromatic amine or alkylamine, preferably ethylenediamine, benzene two
Amine or tripolycyanamide；The concentration of organic amine can be 0.05-10 mg/mL, such as 0.2mg/mL；
D. walk vertical one layer of graphene oxide B of pull-up the described water surface with material II from a, after drying, obtain organic amine layer with upper
The sandwich composite that the graphene oxide A and graphene oxide B of lower floor are covalently bound；
The most optionally, repeat step b-d, make the number of plies increasing of the covalently bound sandwich composite of organic amine and graphene oxide
Add；
F. by upper step gained sandwich composite, with aqueous acetone solution moistening to material deliquescing, then with acetone soak material extremely
Its filter membrane is completely dissolved, and obtains material IV；This step operation is clear state to acetone solution, can be considered that filter membrane is completely dissolved
Fall, it is possible to by detection material IV outward appearance especially transparency to confirm；
G. the graphene oxide in reducing material IV, obtains the graphene film of self-supporting electrically conducting transparent.
Aforementioned " vertical pull-up " means to pull direction to be perpendicular to the water surface；
The number of plies in step e refers to the number of plies of sandwich structure, namely the number of plies of melamine layer, the inventors discovered that, the number of plies is the most,
The mechanical strength of material is the biggest.
Preferably, in aqueous acetone solution described in step f, the volume fraction of acetone is 50-70%, more preferably 60%.
Preferably, the time of aqueous acetone solution moistening described in step f was the 8-12 second, such as 10 seconds.
Preferably, Langmuir-Blodgett method described in step a includes dripping the butanol solution of graphene oxide
On the water surface, this butanol solution can be prepared by ultrasonic；In butanol solution, the concentration of graphene oxide can be 0.01-1
Mg/mL, more preferably 0.02 mg/mL.
Preferably, the final surface pressing when extruded anisotropic graphite alkene of the Langmuir-Blodgett method described in described step a
For 20-30mN/m2, more preferably 25mN/m2；
The extrusion speed of Langmuir-Blodgett method can be 1-10 mm/min, such as 5mm/min.
Preferably, the reducing agent that described reduction reaction uses is hydroiodic acid, hydrazine hydrate or sodium borohydride, and reaction temperature is
25-100 oC, as 40oC、60oC or 100oC。
Preferably, after step g also includes that reduction is anti-, with quoit, the material after reduction is pulled out from its cleaning solvent,
Removing quoit, obtain the graphene film of self-supporting electrically conducting transparent, described quoit can be made up of copper cash, aluminum steel or gold thread；
Alternatively, before removing quoit, being dried by material, described dry temperature is 20-45oC, humidity is 20-60 %, excellent
It is selected in 40oIt is dried under conditions of C, humidity 50%.
As example, the preparation method of graphene oxide raw material used, can be:
A1. being joined in strong acid by the mixture of graphite flakes and nitrate and pre-oxidize, stirring obtains dispersion liquid, then adds
Enter strong oxidizer, stirring, place 1-10 days, obtain the pastel of taupe；
A2. in the pastel of the taupe of a1, it is sequentially added into deionized water and hydrogen peroxide, obtains glassy yellow suspension, to this
Secondary jonquilleous suspension is centrifuged, washs and dialyses, and obtains graphene oxide suspension.
On the other hand, the invention provides the Graphene of a kind of self-supporting electrically conducting transparent obtained by above-mentioned preparation method
The thin film being assembled into.
The main advantage of the present invention is:
The method that the present invention provides, employs organic amine, can serve good hinge effect between graphene sheet layer, strengthens
The mechanical performance of thin film, makes thin film not cracky in operating process；The present invention will remove before reduction in substrate, removes base
The method at the end then, first passes through moistening and plays the effect of " punching ", then changes dicyandiamide solution and thoroughly remove substrate, avoids further
Breakage of thin film applied；These characteristics also makes entirety step of the present invention simple, and operation is simple, the thin film prepared can very big and
Thin, there is high light transmission, good pliability and electric conductivity simultaneously.
Detailed description of the invention
Below in conjunction with embodiment, the detailed description of the invention of the present invention is described in further detail.Following example be for
Further illustrate the present invention, but be not limited to the scope of the present invention.
Embodiment 1
(1) NaNO of 5.00g graphite flake and 3.75g is weighed3In the beaker of 1L, it is stirred, is slowly added to the dense sulfur of 160mL
Acid, stirs 0.5h, is slowly added to the KMnO of 20g4, 40min adds, and stirs into pasty state；After continuing stirring 20h, the most molten
Liquid is aubergine, is mingled with a small amount of paillette；Place 5 days, period manual stirring reactant once in a while；It is slowly added to 500mL deionization
Water, stirring while adding；It is slowly added to 30mL H2O2, now color change is more apparent, now has a large amount of bubble to emerge, is centrifuged, washes
Wash, collect upper strata centrifugal liquid, continue lower sediment to add water-dispersible being centrifuged, collect upper strata centrifugal liquid, the most repeatedly, by collect
Upper strata centrifugal liquid merges, and then dialyses with the bag filter that molecular weight is 8000-14000, just obtains the oxidation stone of high concentration
Ink alkene, uses the graphene oxide of cryodesiccated this concentration of technical calibration, then takes the graphene oxide of a small amount of high concentration,
It is the weak solution that solvent is configured to 0.02mg/ml with n-butyl alcohol, with the ultrasonic 1h of 100W ultrasonic machine, obtains graphene oxide dispersion
Liquid.
(2) take the graphene oxide dispersion of the 0.02mg/mL that 10mL n-butyl alcohol is solvent, delay with 1mL microsyringe
Slowly being added drop-wise to the flume surface of LB instrument, after standing 2 hours under room temperature, the extrusion speed arranging LB instrument is 5mm/min, extruding
Final surface pressing value be 25 mN/m, prepare graphene oxide membrane layer.Then micro-by the water system mixed cellulose ester of 450nm
Hole filter membrane (being produced by Asia, upper Haixing County scavenging material factory, be made up of diacetate fiber and cellulose nitrate, diacetate fiber accounts for 52% ~
57%), from LB tank, it is perpendicular to the water surface one layer of graphene oxide membrane of pull-out, slowly dries up, obtain composite I；Then will be multiple
Condensation material I is immersed in the melamine solution that concentration is 0.2mg/ml 10 seconds, slowly dries up, obtain composite after pulling out
II；In LB groove, it is perpendicular to the water surface one layer of graphene oxide membrane of pull-out with material II again, slowly dries up, obtain two-layer graphite oxide
The sandwich composite (herein referred as monolayer sandwich structure) that alkene is covalently bound with tripolycyanamide；Sandwich composite at water and
The volume ratio of acetone be 2:3 mixed solvent in moistening 10 seconds, transfer to the most at once, in the pure acetone soln of 50ml, soak continuously
Bubble 6h also often changes acetone soln, until acetone soln is by the state of muddiness extremely clarification, is completely dissolved substrate, obtains 20nm
Graphene oxide/melamine film the IV of 6cm/ width 5cm thick, long, transparency is 91%.
(3) redox graphene/melamine film IV:
Configuration acetone: the volume ratio of hydriodic acid aqueous solution is the mixed solvent 50ml of 1:10, lucifuge, 100oUnder C, reduction-oxidation
After Graphene/melamine film IV 10h, take out, slowly clean the thin film reduced with ethanol, then with a copper cash gold
Belong to circle thin film is pulled out from ethanol solution, and be 40 in temperatureoC, humidity be 50% space in dry film, final
Graphene/melamine film that thick to 22nm, the wide 5cm of long 6cm/, transparency reach 83%, square resistance is 420 Europe/square,
Measuring mechanical property stress has reached 46Mpa.
Embodiment 2
Repeat embodiment 1, differ only in: use different organic amine solution to soak, such as ethamine, ethylenediamine or benzene respectively
Diamidogen.
It was found that in the case of the most only 1 layer of organic amine of folder, use ethamine to soak, except substrate
Time, material can be damaged, and uses ethylenediamine or phenylenediamine, all will not be damaged at whole process in which materials.
Embodiment 3
Repeat embodiment 1, following difference: the number of plies of prepared sandwich composite (or being sandwich structure) is different, i.e.
On the basis of the monolayer sandwich structure of embodiment 1, continue combined oxidation graphene layer/melamine layer/graphene oxide layer,
Obtaining the material of 2 layers, 3 layers, 4 layers sandwich structure, wherein the material of 2 layers of sandwich structure includes 3 layers of graphene oxide layer and is clipped in
2 layers of melamine layer therein.
It was found that either graphene oxide/melamine film IV, or final Graphene/tripolycyanamide is thin
Film product, the number of plies is the most, and the mechanical strength of material is the biggest.
Embodiment 4
Repeat embodiment 1, following difference: the temperature of redox graphene/melamine film IV is different, be respectively
Room temperature, 60oC。
Graphene after the reduction finally given/melamine film product, corresponding square resistance has difference, depends on
Secondary is 1250 Europe/square, 840 Europe/square, and the temperature i.e. processed is the highest, can be the least in the square resistance of thin film.
Comparative example:
1, repeat embodiment 1, differ only in and do not soak in the solution of the organic amines such as tripolycyanamide, be i.e. grapheme material
In be not mingled with organic amine, it was found that remove substrate time, material is the most damaged；
Continue test (not the most being mingled with organic amine) along this thinking, increase the number of plies of Graphene further, it was found that work as graphite
Under conditions of the alkene number of plies is 3 layers, remove substrate time, material is not easy breakage, but in subsequent step, material is the most damaged, only when
The Graphene number of plies be 4 layers and above under conditions of, in removing substrate or subsequent step, material is the most all not easy breakage, graphite
When the alkene number of plies is 4 layers, the mechanical test stress of corresponding final products is not higher than 30Mpa；
And embodiment 1 only includes the material of 2 layer graphenes, i.e. will not be damaged, when the Graphene number of plies is 4 layers, corresponding
The mechanical test stress of finished product is 54 Mpa, is significantly larger than 30Mpa when not pressing from both sides organic amine.
2, repeating embodiment 1, differ only in, the solvent of moistening is different, and the volume ratio i.e. arranging water and acetone is respectively
0:5(i.e. pure acetone), 1:4,4:1,5:0(i.e. pure water), during it was found that volume ratio is 4:1,5:0, substrate all can not Ex-all,
And when being 4:1,5:0, reaction is excessively fierce, it is impossible to obtain complete large stretch of graphene oxide/melamine film IV.
3, repeating embodiment 1, differ only in, the final surface pressing value of the extruding that LB instrument is arranged is 35 mN/m, knot
Fruit finds, the graphene oxide excessive extrusion that LB instrument prepares, and between lamella, stacking or buckling phenomena are the most serious.
4, embodiment 1, following difference: the solvent that step (1) is prepared used by graphene oxide dispersion changes are repeated
Become the mixed solvent of the different volumes ratio of isopropanol, water, methanol or its two-two mixing.
Found that:
When use water is solvent, graphene oxide dispersion is directly miscible in whole tank, and experiment cannot be carried out；Use first
When alcohol, isopropanol, methanol/isopropanol, alcohol/water are solvent, graphene oxide dispersion can occur reuniting and dividing in flume surface
Dissipating uneven phenomenon, the thin-film material ultimately resulting in preparation is in uneven thickness, affects transparency, conduction and mechanical performance.
Further study show that, compared with these dicyandiamide solutions, when embodiment 1 uses pure butanol to be solvent, dispersion liquid
Zeta potential value minimum.
Claims (10)
1. a preparation method for self-supporting transparent conductive graphene membrane, comprises the following steps:
A. Langmuir-Blodgett method prepares graphene oxide layer on the water surface；
B. with filter membrane vertical one layer of graphene oxide A of pull-up from the water surface, the material I that filter membrane is compound with graphene oxide A is obtained,
The water system microporous filter membrane that described filter membrane is cellulose nitrate and acetate fiber is made；
C., b walks resulting materials I soak in the aqueous solution of organic amine, make the surface of graphene oxide A covalently bound have organic
Amine layer, prepares the material II that filter membrane, graphene oxide and organic amine are compound, and described organic amine is macromolecule polyalcohol or little molecule
Organic substance, and each molecule is with plural amino or imino group；
D. walk vertical one layer of graphene oxide B of pull-up the described water surface with material II from a, after drying, obtain organic amine layer with upper
The sandwich composite that the graphene oxide A and graphene oxide B of lower floor are covalently bound；
The most optionally, repeat step b-d, make the number of plies increasing of the covalently bound sandwich composite of organic amine and graphene oxide
Add；
F. by upper step gained sandwich composite, with aqueous acetone solution moistening to material deliquescing, then with acetone soak material extremely
Its filter membrane is completely dissolved, and obtains material IV；
G. the graphene oxide in reducing material IV, obtains the graphene film of self-supporting electrically conducting transparent.
2. preparation method as claimed in claim 1, is characterized in that, in aqueous acetone solution described in step f, and the volume fraction of acetone
For 50-70%, preferably 60%.
3. preparation method as claimed in claim 1, is characterized in that, the time of aqueous acetone solution moistening described in step f is 8-12
Second, preferably 10 seconds.
4. preparation method as claimed in claim 1, is characterized in that, described organic amine is aromatic amine or alkylamine, as ethylenediamine,
Phenylenediamine or tripolycyanamide.
5. preparation method as claimed in claim 1, is characterized in that, in the aqueous solution of organic amine described in step c, and organic amine dense
Degree is 0.05-10 mg/mL, preferably 0.2mg/mL.
6. preparation method as claimed in claim 1, is characterized in that, Langmuir-Blodgett method described in step a include by
The butanol solution of graphene oxide is added drop-wise on the water surface, and preferably in butanol solution, the concentration of graphene oxide is 0.01-1
Mg/mL, more preferably 0.02 mg/mL.
7. preparation method as claimed in claim 1, is characterized in that, described in described step a, Langmuir-Blodgett method exists
Final surface pressing during extruded anisotropic graphite alkene is 20-30mN/m2, preferably 25mN/m2。
8. preparation method as claimed in claim 1, is characterized in that, the reducing agent that described reduction reaction uses is hydroiodic acid, water
Closing hydrazine or sodium borohydride, reaction temperature is 25-100oC, preferably 40oC、60oC or 100oC。
9. preparation method as claimed in claim 1, is characterized in that, after step g also includes that reduction is anti-, after reducing with quoit
Material pull out from its cleaning solvent, remove quoit, obtain the graphene film of self-supporting electrically conducting transparent；Alternatively, go
Before quoit, being dried by material, described dry temperature is 20-45oC, humidity is 20-60 %, preferably 40oC、
It is dried under conditions of humidity 50%.
10. the graphene film that any one of claim 1-9 preparation method prepares.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637925A (en) * | 2017-03-17 | 2017-05-10 | 苏州佰锐生物科技有限公司 | Preparation method of anti-ultraviolet cotton fabric with graphene oxide monomolecular coating |
| CN107791614A (en) * | 2017-10-13 | 2018-03-13 | 南京旭羽睿材料科技有限公司 | The preparation of graphene composite film and its processing technology |
| CN109859999A (en) * | 2019-01-23 | 2019-06-07 | 盐城师范学院 | LB embrane method prepares grid of transmission electronic microscope |
| CN115072714A (en) * | 2022-06-07 | 2022-09-20 | 苏州大学 | Amine compound modified graphene film and preparation method thereof |
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| CN103497437A (en) * | 2013-10-21 | 2014-01-08 | 山东科技大学 | Light high-strength brominated butyl rubber airtight material and preparation method and application thereof |
| CN104530775A (en) * | 2014-12-25 | 2015-04-22 | 江南大学 | Preparation method of graphene nanofiller for epoxy molding compound modification |
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2016
- 2016-08-03 CN CN201610630029.7A patent/CN106276872B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497437A (en) * | 2013-10-21 | 2014-01-08 | 山东科技大学 | Light high-strength brominated butyl rubber airtight material and preparation method and application thereof |
| CN104530775A (en) * | 2014-12-25 | 2015-04-22 | 江南大学 | Preparation method of graphene nanofiller for epoxy molding compound modification |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637925A (en) * | 2017-03-17 | 2017-05-10 | 苏州佰锐生物科技有限公司 | Preparation method of anti-ultraviolet cotton fabric with graphene oxide monomolecular coating |
| CN107791614A (en) * | 2017-10-13 | 2018-03-13 | 南京旭羽睿材料科技有限公司 | The preparation of graphene composite film and its processing technology |
| CN109859999A (en) * | 2019-01-23 | 2019-06-07 | 盐城师范学院 | LB embrane method prepares grid of transmission electronic microscope |
| CN109859999B (en) * | 2019-01-23 | 2021-01-12 | 盐城师范学院 | Method for preparing transmission electron microscope carrier net by LB membrane method |
| CN115072714A (en) * | 2022-06-07 | 2022-09-20 | 苏州大学 | Amine compound modified graphene film and preparation method thereof |
| CN115072714B (en) * | 2022-06-07 | 2023-10-13 | 苏州大学 | Amine compound modified graphene film and preparation method thereof |
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