CN108039221B - Flexible transparent conductive film and preparation method thereof - Google Patents
Flexible transparent conductive film and preparation method thereof Download PDFInfo
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- CN108039221B CN108039221B CN201711227567.2A CN201711227567A CN108039221B CN 108039221 B CN108039221 B CN 108039221B CN 201711227567 A CN201711227567 A CN 201711227567A CN 108039221 B CN108039221 B CN 108039221B
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- -1 graphene compound Chemical class 0.000 claims abstract description 172
- 238000000034 method Methods 0.000 claims abstract description 160
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 239000010408 film Substances 0.000 claims description 159
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- 238000006137 acetoxylation reaction Methods 0.000 claims description 66
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- IYGAMTQMILRCCI-UHFFFAOYSA-N 3-aminopropane-1-thiol Chemical compound NCCCS IYGAMTQMILRCCI-UHFFFAOYSA-N 0.000 description 1
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- 108010024636 Glutathione Proteins 0.000 description 1
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- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical compound [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The present invention provides a kind of flexible transparent conductive film and preparation method thereof.The production method of flexible transparent conductive film of the invention, as conductive filler, makes flexible transparent conductive film resistant to bending using Lang Gemiaoer-Buji spy's method using silver nanowires-reduced graphene compound and non-reduced method graphene；The silver nanowires-reduced graphene compound after reduced graphene is modified by obtaining silver nanowires, there are π-π effects between the silver nanowires-reduced graphene compound and non-reduced method graphene, improve the synergistic effect between conductive filler, therefore flexible transparent conductive film produced by the present invention has very excellent mechanical stability and electric conductivity, even across 1500 times or more bendings, it is still able to maintain very high conductivity.
Description
Technical field
The present invention relates to field of display technology more particularly to a kind of flexible transparent conductive film and preparation method thereof.
Background technique
In recent years, flexible transparent conductive film is as a kind of film for having both electric conductivity, translucency, bending resistance,
It is widely used in the field of photoelectric devices such as liquid crystal display, touch screen, Organic Light Emitting Diode, solar battery.Common is soft
Property transparent conductive film is mainly tin indium oxide (ITO) film, metal mesh diaphragm, nano-silver thread film, graphene film etc., wherein aoxidizing
Indium tin membrane technology is mature, but have the shortcomings that cost of material height, electric conductivity there are the limit, it is not resistant to bending；Although metal grill film
Low in raw material price, and electromagnetism interference, but have the shortcomings that metal line width is larger and there is unauspicious interference.
Currently, silver nanowires (AgNWs) is since line width is smaller and prepares conductive film with sheet resistance is low, light transmittance with it
Advantage high, resistant to bending is suitble to production flexible electronic device, uniquely unfortunately increases when to reduce the resistance value of conductive film
After big silver nanowires dosage, the transparency of conductive film is remarkably decreased.
Graphene is a kind of emerging conductive filler, with flexibility is good, electric conductivity is outstanding, chemical stability is excellent and knot
The advantages that structure performance is controllable, it is rapid in flexible conducting material field application development in recent years, the conduction prepared with graphene
Film has many advantages, such as film transparency height, infrared permeable, resistant to bending, is suitble to production flexible electronic device, however its raw material at
This is excessively high, and large scale technology is not yet realized.
In general, indium oxide tin film and metal mesh diaphragm are not suitable for production fexible film device, single silver nanowire film
It is difficult to take into account electric conductivity and the transparency, and single graphene film then cannot be considered in terms of low preparation cost and high conductivity.There is research
It attempts to reduced graphene (r-GO) being mixed with silver nanowires/reduced graphene (AgNWs/r-GO) with silver nanowires compound
Film helps to improve the electric conductivity of graphene film to play conducting bridge beam action between graphene crystal boundary for silver nanowires,
And it is smaller on translucency influence, but further study show that, there is no phase interactions between two kinds of fillers of silver nanowires and graphene
With both being unable to give full play out the advantages of should having, therefore the synergistic effect between two kinds of fillers of silver nanowires and graphene has
Wait further increase.
Existing preparation silver nanowires/reduced graphene composite membrane method mainly has spin-coating method, spray coating method, bar film
Special (Langmuir-Blodgett, L-B) method of method, Lang Gemiaoer-Buji etc., wherein L-B method is simple, and by functional molecular
The limitation of molecular structure influences very little.
Summary of the invention
The purpose of the present invention is to provide a kind of production methods of flexible transparent conductive film, using silver nanowires-reduction
Graphene complex and non-reduced method graphene are made resistant to bending soft using Lang Gemiaoer-Buji spy's method as conductive filler
Property transparent conductive film, flexible transparent conductive film obtained have very excellent mechanical stability and electric conductivity.
The object of the invention is also to provide a kind of flexible transparent conductive film, with very excellent mechanical stability with
Electric conductivity.
To achieve the above object, the present invention provides a kind of production method of flexible transparent conductive film, includes the following steps:
Step 1, preparation silver nanowires-reduced graphene compound, the silver nanowires-reduced graphene compound include
One of amination silver nanowires-reduced graphene compound and acetoxylation silver nanowires-reduced graphene compound are a variety of；
The structural formula of the amination silver nanowires-reduced graphene compound isInstitute
Stating acetoxylation silver nanowires-reduced graphene compound structural formula is
In two above structural formula, the vertical thick line among structural formula indicates silver nanowires, and rGO indicates reduction graphite
Alkene；
Step 2 disperses silver nanowires made from step 1-reduced graphene compound in the first organic solvent, obtains
Silver nanowires-reduced graphene complex solution；By non-reduced method graphene dispersion in the second organic solvent, obtain non-reduced
Method graphene solution；Silver nanowires-reduced graphene complex solution is uniformly mixed with non-reduced method graphene solution, is obtained
Silver nanowires-reduced graphene compound/non-reduced method graphene solution；
Step 3 provides non-transparent flexible substrate, also using silver nanowires made from step 2-reduced graphene compound/non-
Former method graphene solution is respectively formed at least two layers of silver nanoparticle in non-transparent flexible substrate two sides by Lang Gemiaoer-Buji spy method
Line-reduced graphene compound/non-reduced method graphene film, obtains flexible transparent conductive film.
The preparation method of the amination silver nanowires-reduced graphene compound includes the following steps:
Silver nanowires, mercapto-amine, deionized water are added in reaction vessel and are uniformly mixed by step 11, obtain mixed liquor, right
Mixed liquor carries out centrifugation and removes supernatant, after cleaning lower sediment thing using deionized water, using deionized water to lower sediment thing
Dispersed, obtains amination silver nanowires aqueous solution；
Graphene oxide powder is added in deionized water step 12, boils and is cooled to 80 DEG C hereinafter, obtaining graphite oxide
Alkene concentrate；
Step 13, by graphene oxide concentrate made from amination silver nanowires aqueous solution made from step 11 and step 12
It is mixed 12 hours or more under the conditions of 48 DEG C~52 DEG C of temperature, it is molten to obtain amination silver nanowires-graphene oxide compound
Liquid；
Reducing agent is added to amination silver nanowires-in step 14 in amination silver nanowires-graphene oxide complex solution
Graphene oxide compound is restored, and amination silver nanowires-reduced graphene complex solution is obtained；
Step 15 be centrifuged to amination silver nanowires-reduced graphene complex solution and removes supernatant, using deionization
After water cleans lower sediment thing, amination silver nanowires-reduced graphene compound is obtained；
The sequence of the step 11 and step 12 can be interchanged.
The preparation method of the acetoxylation silver nanowires-reduced graphene compound includes the following steps:
Step 11 ', will silver nanowires, mercaptoalkyl acid, deionized water be added reaction vessel in be uniformly mixed, mixed
Liquid carries out centrifugation to mixed liquor and removes supernatant, after cleaning lower sediment thing using deionized water, lower sediment thing dried, is obtained
To acetoxylation silver nanowires；
Step 12 ', graphene oxide powder and acetoxylation silver nanowires are added in tetrahydrofuran are uniformly dispersed, add
4-dimethylaminopyridine and acid binding agent, 98 DEG C~102 DEG C back flow reaction 12 hours or more, supernatant is removed in centrifugation, using go from
After sub- water cleaning lower sediment thing, lower sediment thing is dispersed using deionized water, obtains acetoxylation silver nanowires-oxidation
Graphene complex solution；
Step 13 ', in acetoxylation silver nanowires-graphene oxide complex solution be added reducing agent acetoxylation silver is received
Rice noodles-graphene oxide compound is restored, and acetoxylation silver nanowires-reduced graphene complex solution is obtained；
Step 14 ', carry out centrifugation to acetoxylation silver nanowires-reduced graphene complex solution and remove supernatant, using going
After ionized water cleans lower sediment thing, acetoxylation silver nanowires-reduced graphene compound is obtained.
The step 3 includes:
Step 31 disperses silver nanowires made from step 2-reduced graphene compound/non-reduced method graphene solution
In in water parfacies, silver nanowires-reduced graphene compound/non-reduced method graphene film is formed in water parfacies, it will be transparent
Flexible substrates, which are inserted vertically into, to be dispersed in silver nanowires-reduced graphene compound/non-reduced method graphene film water parfacies,
Lifting upwards, makes the two sides of non-transparent flexible substrate adhere to one layer of silver nanowires-reduced graphene compound/non-reduced method stone respectively
Black alkene film, obtains the first composite conductive thin film；
Step 32, using Lang Gemiaoer-Buji spy method first composite conductive thin film two sides adhere to respectively one layer or
One layer or more of silver nanowires-reduced graphene compound/non-reduced method graphene film forms silver nanowires-reduction graphite
Alkene composite conductive thin film.
The present invention also provides flexible and transparent conductives made from a kind of production method using above-mentioned flexible transparent conductive film
Film, including non-transparent flexible substrate and be attached to several layers of silver nanowires-reduced graphene compounds of non-transparent flexible substrate two sides/
Non-reduced method graphene film；The silver nanowires-reduced graphene compound/non-reduced method graphene film material includes
The silver nanowires mixed-reduced graphene compound and non-reduced method graphene；Described several layers indicate two layers or two layers
More than；
The silver nanowires-reduced graphene compound includes amination silver nanowires-reduced graphene compound and acetic acid
Change one of silver nanowires-reduced graphene compound or a variety of；
The structural formula of the amination silver nanowires-reduced graphene compound isInstitute
Stating acetoxylation silver nanowires-reduced graphene compound structural formula is
In two above structural formula, the vertical thick line among structural formula indicates silver nanowires, and rGO indicates reduction graphite
Alkene.
The present invention also provides the production methods of another flexible transparent conductive film, include the following steps:
Step 10, preparation silver nanowires-reduced graphene compound, the silver nanowires-reduced graphene compound packet
Include one of amination silver nanowires-reduced graphene compound and acetoxylation silver nanowires-reduced graphene compound or more
Kind；
The structural formula of the amination silver nanowires-reduced graphene compound isInstitute
Stating acetoxylation silver nanowires-reduced graphene compound structural formula is
In two above structural formula, the vertical thick line among structural formula indicates silver nanowires, and rGO indicates reduction graphite
Alkene；
Step 20 disperses silver nanowires made from step 10-reduced graphene compound in third organic solvent, obtains
Disperse solution to silver nanowires-reduced graphene compound；By the silver nanowires-reduced graphene compound dispersion solution with
4th organic solvent is uniformly mixed, and obtains silver nanowires-reduced graphene complex solution；
Step 30 provides non-transparent flexible substrate, utilizes silver nanowires made from step 20-reduced graphene complex solution
It is multiple that in non-transparent flexible substrate two sides at least two layers silver nanowires-reduced graphene is respectively formed by Lang Gemiaoer-Buji spy method
Object film is closed, silver nanowires-reduced graphene composite conductive thin film is formed；
Step 40, the non-reduced method graphene of offer obtain non-by non-reduced method graphene dispersion in the 5th organic solvent
Reduction method graphene solution；
Step 50, the silver nanowires-reduced graphene composite conductive thin film prepared using step 30 utilize step 40 as substrate
Non-reduced method graphene solution obtained is thin in silver nanowires-reduced graphene composite conducting by Lang Gemiaoer-Buji spy method
Film two sides are respectively formed at least two layers non-reduced method graphene film, obtain flexible transparent conductive film.
The preparation method of the amination silver nanowires-reduced graphene compound includes the following steps:
Silver nanowires, mercapto-amine, deionized water are added in reaction vessel and are uniformly mixed by step 11, obtain mixed liquor, right
Mixed liquor carries out centrifugation and removes supernatant, after cleaning lower sediment thing using deionized water, using deionized water to lower sediment thing
Dispersed, obtains amination silver nanowires aqueous solution；
Graphene oxide powder is added in deionized water step 12, boils and is cooled to 80 DEG C hereinafter, obtaining graphite oxide
Alkene concentrate；
Step 13, by graphene oxide concentrate made from amination silver nanowires aqueous solution made from step 11 and step 12
It is mixed 12 hours or more under the conditions of 48 DEG C~52 DEG C of temperature, it is molten to obtain amination silver nanowires-graphene oxide compound
Liquid；
Reducing agent is added to amination silver nanowires-in step 14 in amination silver nanowires-graphene oxide complex solution
Graphene oxide compound is restored, and amination silver nanowires-reduced graphene complex solution is obtained；
Step 15 be centrifuged to amination silver nanowires-reduced graphene complex solution and removes supernatant, using deionization
After water cleans lower sediment thing, amination silver nanowires-reduced graphene compound is obtained.
The preparation method of the acetoxylation silver nanowires-reduced graphene compound includes the following steps:
Step 11 ', will silver nanowires, mercaptoalkyl acid, deionized water be added reaction vessel in be uniformly mixed, mixed
Liquid carries out centrifugation to mixed liquor and removes supernatant, after cleaning lower sediment thing using deionized water, lower sediment thing dried, is obtained
To acetoxylation silver nanowires；
Step 12 ', graphene oxide powder and acetoxylation silver nanowires are added in tetrahydrofuran are uniformly dispersed, add
4-dimethylaminopyridine and acid binding agent, 98 DEG C~102 DEG C back flow reaction 12 hours or more, supernatant is removed in centrifugation, using go from
After sub- water cleaning lower sediment thing, lower sediment thing is dispersed using deionized water, obtains acetoxylation silver nanowires-oxidation
Graphene complex solution；
Step 13 ', in acetoxylation silver nanowires-graphene oxide complex solution be added reducing agent acetoxylation silver is received
Rice noodles-graphene oxide compound is restored, and acetoxylation silver nanowires-reduced graphene complex solution is obtained；
Step 14 ', carry out centrifugation to acetoxylation silver nanowires-reduced graphene complex solution and remove supernatant, using going
After ionized water cleans lower sediment thing, acetoxylation silver nanowires-reduced graphene compound is obtained.
The step 30 includes:
Step 310 disperses silver nanowires made from step 20-reduced graphene complex solution in water parfacies,
Silver nanowires-reduced graphene complex thin film is formed in water parfacies, and non-transparent flexible substrate is inserted vertically into and is dispersed with silver nanoparticle
In line-reduced graphene complex thin film water parfacies, lifts upwards, the two sides of non-transparent flexible substrate is made to adhere to one layer of silver respectively
Nano wire-reduced graphene complex thin film, obtains the second composite conductive thin film；
Step 320 adheres to one layer in the two sides of second composite conductive thin film using Lang Gemiaoer-Buji spy method respectively
Or one layer or more of silver nanowires-reduced graphene complex thin film, it is thin to form silver nanowires-reduced graphene composite conducting
Film；
The step 50 includes:
Step 510 disperses non-reduced method graphene solution made from step 40 in water parfacies, is formed in water parfacies
Silver nanowires-reduced graphene composite conductive thin film is inserted vertically into and is dispersed with non-reduced method stone by non-reduced method graphene film
In the water parfacies of black alkene film, lifts upwards, silver nanowires-reduced graphene composite conductive thin film two sides is made to adhere to one respectively
The non-reduced method graphene film of layer, obtains third composite conductive thin film；
Step 520 adheres to one layer in the two sides of the third composite conductive thin film using Lang Gemiaoer-Buji spy method respectively
Or one layer or more of non-reduced method graphene film, obtain flexible transparent conductive film.
The present invention also provides flexible and transparent conductives made from a kind of production method using above-mentioned flexible transparent conductive film
Film including non-transparent flexible substrate, is attached respectively to several layers of silver nanowires-reduced graphene of the non-transparent flexible substrate two sides
Complex thin film is located on several layers of silver nanowires-reduced graphene complex thin film of the non-transparent flexible substrate two sides
Several layers of non-reduced method graphene film；Described two layers or two layers of several layers of expression or more；
The silver nanowires-reduced graphene compound includes amination silver nanowires-reduced graphene compound and acetic acid
Change one of silver nanowires-reduced graphene compound or a variety of；
The structural formula of the amination silver nanowires-reduced graphene compound isInstitute
Stating acetoxylation silver nanowires-reduced graphene compound structural formula is
In two above structural formula, the vertical thick line among structural formula indicates silver nanowires, and rGO indicates reduction graphite
Alkene.
Beneficial effects of the present invention: the production method of flexible transparent conductive film of the invention uses silver nanowires-reduction
Graphene complex and non-reduced method graphene are made resistant to bending soft using Lang Gemiaoer-Buji spy's method as conductive filler
Property transparent conductive film；The silver nanowires-reduced graphene compound is by modifying silver nanowires by reduced graphene
After obtain, there are π-π effect between the silver nanowires-reduced graphene compound and non-reduced method graphene, improve and lead
Synergistic effect between electric filler；The performance of flexible transparent conductive film obtained better than existing tin indium oxide conductive film,
Silver nanowires conductive film, silver nanowires/reduced graphene composite membrane have very excellent mechanical stability and electric conductivity,
Even across 1500 times or more bendings, it is still able to maintain very high conductivity.Flexible transparent conductive film of the invention is using silver
Nano wire-reduced graphene compound and non-reduced method graphene are as conductive filler, since silver nanowires-reduced graphene is multiple
It closes between object and non-reduced method graphene there are π-π effect, the synergistic effect between conductive filler is improved, so that of the invention
Flexible transparent conductive film has very excellent electric conductivity and mechanical stability.
For further understanding of the features and technical contents of the present invention, it please refers to below in connection with of the invention detailed
Illustrate and attached drawing, however, the drawings only provide reference and explanation, is not intended to limit the present invention.
Detailed description of the invention
With reference to the accompanying drawing, by the way that detailed description of specific embodiments of the present invention, technical solution of the present invention will be made
And other beneficial effects are apparent.
In attached drawing,
Fig. 1 is the flow chart of the first embodiment of the production method of flexible transparent conductive film of the invention；
Fig. 2 is the schematic diagram for depositing film forming in substrate using Lang Gemiaoer-Buji spy's method；
Fig. 3 is the flow chart of the second embodiment of the production method of flexible transparent conductive film of the invention.
Specific embodiment
Further to illustrate technological means and its effect adopted by the present invention, below in conjunction with preferred implementation of the invention
Example and its attached drawing are described in detail.
Referring to Fig. 1, the first embodiment of the production method for flexible transparent conductive film of the invention, including walk as follows
It is rapid:
Step 1, preparation silver nanowires-reduced graphene (AgNWs-rGO) compound, the silver nanowires-reduction graphite
Alkene compound includes in amination silver nanowires-reduced graphene compound and acetoxylation silver nanowires-reduced graphene compound
It is one or more；
The structural formula of the amination silver nanowires-reduced graphene compound isInstitute
Stating acetoxylation silver nanowires-reduced graphene compound structural formula is
In two above structural formula, the vertical thick line among structural formula indicates silver nanowires, and rGO indicates reduction graphite
Alkene.In various structural formulas involved in hereafter, vertical thick line is identical as the meaning that rGO is indicated.
Specifically, the reduced graphene (rGO) is the product that graphene oxide (GO) is obtained after electronation.
Specifically, the preparation method of the amination silver nanowires-reduced graphene compound includes the following steps:
Silver nanowires, mercapto-amine, deionized water are added in reaction vessel and are uniformly mixed by step 11, obtain mixed liquor, right
Mixed liquor carries out centrifugation and removes supernatant, after cleaning lower sediment thing using deionized water, using deionized water to lower sediment thing
Dispersed, obtains amination silver nanowires aqueous solution.
Specifically, the structural formula of the amination silver nanowires is
Specifically, silver nanowires, mercapto-amine, deionized water are added in reaction vessel and are uniformly mixed in the step 11
Method are as follows: silver nanowires, mercapto-amine, deionized water are added in reaction vessel and under the conditions of 25 DEG C~50 DEG C temperature stir 6
Hour or more.
Specifically, in the step 11, be added the silver nanowires in reaction vessel and mercapto-amine molar ratio be 1:2~
30。
Specifically, the mercapto-amine include Mercamine Cysteamine, 3- sulfydryl -1- propylamine, p-Mercaptoaniline, L-cysteine,
One of glutathione, amino mercapto thiadiazoles, 3- amino -5- sulfydryl -1,2,4- triazole are a variety of.
Graphene oxide (GO) powder is added in deionized water step 12, boils and is cooled to 80 DEG C hereinafter, being aoxidized
Graphene concentrate.
Specifically, the purpose boiled is to remove the oxygen dissolved in graphene oxide water solution in the step 12, keep away
Exempting from oxygen influences subsequent chemical reaction.
Step 13, by graphene oxide concentrate made from amination silver nanowires aqueous solution made from step 11 and step 12
It is mixed 12 hours or more under the conditions of 48 DEG C~52 DEG C of temperature, it is molten to obtain amination silver nanowires-graphene oxide compound
Liquid.
Preferably, in the step 13, by oxygen made from amination silver nanowires aqueous solution made from step 11 and step 12
Graphite alkene concentrate is mixed under the conditions of 50 DEG C of temperature.
Specifically, in the step 13, by oxygen made from amination silver nanowires aqueous solution made from step 11 and step 12
Graphite alkene concentrate is mixed according to the ratio that graphene oxide and the mass ratio of amination silver nanowires are 1:1-100.
Specifically, the reaction equation of the step 13 is as follows:
In above-mentioned reaction equation,Indicate graphene oxide,Indicate that amination silver is received
Rice noodles-graphene oxide compound.
Reducing agent is added to amination silver nanowires-in step 14 in amination silver nanowires-graphene oxide complex solution
Graphene oxide compound is restored, and amination silver nanowires-reduced graphene complex solution is obtained.
Specifically, the reducing agent includes one of glucose, hydroiodic acid, hydrazine hydrate or a variety of in the step 14.
Specifically, reducing agent pair is added in amination silver nanowires-graphene oxide complex solution in the step 14
The operating procedure that amination silver nanowires-graphene oxide compound is restored are as follows: multiple in amination silver nanowires-graphene oxide
Reducing agent is added in polymer solution, is stirred 1 hour or more under the conditions of 25 DEG C~50 DEG C of temperature.
Specifically, the reaction equation of the step 14 is as follows:
In above-mentioned reaction equation,Indicate that amination silver nanowires-reduced graphene is compound
Object.
Step 15 be centrifuged to amination silver nanowires-reduced graphene complex solution and removes supernatant, using deionization
After water cleans lower sediment thing, amination silver nanowires-reduced graphene compound is obtained.
Specifically, the step 15 further include: be stored in amination silver nanowires-reduced graphene compound standby in ethyl alcohol
With.
In the preparation method of the amination silver nanowires-reduced graphene compound, the step 11 is suitable with step 12
Sequence can be interchanged.
Specifically, the preparation method of the acetoxylation silver nanowires-reduced graphene compound includes the following steps:
Step 11 ', will silver nanowires, mercaptoalkyl acid, deionized water be added reaction vessel in be uniformly mixed, mixed
Liquid carries out centrifugation to mixed liquor and removes supernatant, after cleaning lower sediment thing using deionized water, lower sediment thing dried, is obtained
To acetoxylation silver nanowires.
Specifically, the structural formula of the acetoxylation silver nanowires is
Specifically, the step 11 ' in, silver nanowires, mercaptoalkyl acid, deionized water are added in reaction vessel and are mixed
Uniform method are as follows: silver nanowires, mercaptoalkyl acid, deionized water are added in reaction vessel in 25 DEG C~50 DEG C temperature conditions
Lower stirring 6 hours or more.
Specifically, the step 11 ' in, the molar ratio of the silver nanowires and mercaptoalkyl acid is 1:2~30.
Specifically, the mercaptoalkyl acid includes one of thioacetic acid, mercaptopropionic acid, 4- mercaptobutyric acid or a variety of.
Specifically, the step 11 ' in, lower sediment thing is dried in vacuum environment.
Step 12 ', graphene oxide (GO) powder and acetoxylation silver nanowires are added in tetrahydrofuran are uniformly dispersed, then
4-dimethylaminopyridine (DMAP) and acid binding agent is added, 98 DEG C~102 DEG C back flow reaction 12 hours or more, supernatant is removed in centrifugation
Liquid disperses lower sediment thing using deionized water after cleaning lower sediment thing using deionized water, obtains acetoxylation silver
Nano wire-graphene oxide complex solution.
Specifically, the step 12 ' reaction equation it is as follows:
In above-mentioned reaction equation,Indicate graphene oxide,Indicate that acetoxylation silver is received
Rice noodles-graphene oxide compound.
Specifically, the step 12 ' in, it according to mass ratio is 1:1 by graphene oxide powder and acetoxylation silver nanowires
~100 are added in tetrahydrofuran, are uniformly dispersed by the way of ultrasonic treatment.The ultrasonic treatment is carried out using low-power.
Step 13 ', in acetoxylation silver nanowires-graphene oxide complex solution be added reducing agent acetoxylation silver is received
Rice noodles-graphene oxide compound is restored, and acetoxylation silver nanowires-reduced graphene complex solution is obtained.
Specifically, the step 13 ' in, the reducing agent includes one of glucose, hydroiodic acid, hydrazine hydrate or more
Kind.
Specifically, the step 13 ' in, reduction is added in acetoxylation silver nanowires-graphene oxide complex solution
The operating procedure that agent restores silver nanowires-graphene oxide compound are as follows: in acetoxylation silver nanowires-graphene oxide
Reducing agent is added in complex solution, is stirred 1 hour or more under the conditions of 25 DEG C~50 DEG C of temperature.
Specifically, the step 13 ' reaction equation it is as follows:
In above-mentioned reaction equation,Indicate that acetoxylation silver nanowires-reduced graphene is compound
Object.
Step 14 ', carry out centrifugation to acetoxylation silver nanowires-reduced graphene complex solution and remove supernatant, using going
After ionized water cleans lower sediment thing, acetoxylation silver nanowires-reduced graphene compound is obtained.
Specifically, the step 14 ' further include: acetoxylation silver nanowires-reduced graphene compound is stored in ethyl alcohol
In it is spare.
Step 2 disperses silver nanowires made from step 1-reduced graphene compound in the first organic solvent, obtains
Silver nanowires-reduced graphene complex solution；It disperses non-reduced method graphene (GN) in the second organic solvent, obtains non-
Reduction method graphene solution；Silver nanowires-reduced graphene complex solution is uniformly mixed with non-reduced method graphene solution,
Obtain silver nanowires-reduced graphene compound/non-reduced method graphene (AgNWs-rGO/GN) solution.
Specifically, the silver nanowires-reduced graphene complex solution and non-reduced method graphene solution pass through ultrasound
Processing is uniformly mixed, and the ultrasonic treatment is carried out using low-power.
Specifically, the first organic solvent dissolves each other with the second organic solvent, and second solvent and water are immiscible.It is preferred that
, first solvent is dimethylformamide (DMF)；Second solvent includes one of toluene, methylene chloride, chloroform
Or it is a variety of.
Specifically, the non-reduced method graphene is using the graphene of non-oxide reduction method preparation, including useization
Learn one of graphene made from vapor deposition (CVD) method and graphene made from use mechanical stripping method or a variety of.Institute
Stating non-reduced method graphene has layer structure, described to be usually using graphene made from chemical vapor deposition (CVD) method
Single layer structure, described using graphene made from mechanical stripping method is usually multilayered structure.
Specifically, the thickness using graphene made from chemical vapor deposition method is less than 10nm, using mechanical stripping method
Graphene obtained with a thickness of 0.35~35nm.
Specifically, the silver nanowires-reduced graphene compound/non-reduced method graphene (AgNWs-rGO/GN) solution
Concentration be 0.1-100mg/mL, wherein non-reduced method graphene (GN) and silver nanowires-reduced graphene compound (AgNWs-
RGO mass ratio) is 1:0.1~500.
It is easy to reunite since the piece Interaction between layers of non-reduced method graphene (GN) are strong, therefore non-reduced method graphene is logical
Often dispersion concentration is extremely low in the solution, is prepared using special (Langmuir-Blodgett) law technology of Lang Gemiaoer-Buji non-reduced
The difficulty of method graphene film is larger.The present invention is by silver nanowires-reduced graphene complex solution and non-reduced method graphene
Solution mixes, and interacts by force using between silver nanowires-reduced graphene compound and non-reduced method graphene
Feature increases the dispersion concentration of non-reduced method graphene in the solution, and silver nanowires-reduced graphene compound is non-reduced
The piece interlayer of method graphene plays buffer action, can reduce the reunion of non-reduced method graphene, promotes non-reduced method graphene
Dispersion stabilization in the solution.
Step 3, referring to Fig. 2, provide non-transparent flexible substrate, it is multiple using silver nanowires-reduced graphene made from step 2
Object/non-reduced method graphene solution is closed by special (Langmuir-Blodgett) method of Lang Gemiaoer-Buji in non-transparent flexible substrate
Two sides are respectively formed at least two layers silver nanowires-reduced graphene compound/non-reduced method graphene film, obtain flexible and transparent
Conductive film.
Specifically, the non-transparent flexible substrate can be PET (polyethylene terephthalate) film, PI (polyimides)
The transparent flexible films, preferably PET film such as film, PMMA (polymethyl methacrylate) film or PC (polycarbonate) film.
Specifically, the step 3 includes:
Step 31 disperses silver nanowires made from step 2-reduced graphene compound/non-reduced method graphene solution
In in water parfacies, silver nanowires-reduced graphene compound/non-reduced method graphene film is formed in water parfacies, it will be transparent
Flexible substrates, which are inserted vertically into, to be dispersed in silver nanowires-reduced graphene compound/non-reduced method graphene film water parfacies,
Lifting upwards, makes the two sides of non-transparent flexible substrate adhere to one layer of silver nanowires-reduced graphene compound/non-reduced method stone respectively
Black alkene film, obtains the first composite conductive thin film.
Specifically, the step 31 includes: to provide Langmuir-Blodgett film analysis instrument, silver made from step 2 is received
Rice noodles-reduced graphene compound/non-reduced method graphene solution is infused by the sample of Langmuir-Blodgett film analysis instrument
It penetrates in the water parfacies that auxiliary system is added drop-wise in shallow pond, stands, form silver nanowires-reduced graphene compound/non-reduced method
Graphene film, non-transparent flexible substrate is suspended on Langmuir-Blodgett film analysis instrument and is inserted vertically into be dispersed with silver
In nano wire-reduced graphene compound/non-reduced method graphene film water parfacies, lift upwards, silver nanowires-reduction stone
Black alkene compound/non-reduced method graphene film is attached to non-transparent flexible substrate two sides.
Specifically, the speed that the non-transparent flexible substrate lifts upwards is 1-30mm/min in the step 31.
Step 32, using Lang Gemiaoer-Buji spy method first composite conductive thin film two sides adhere to respectively one layer or
One layer or more of silver nanowires-reduced graphene compound/non-reduced method graphene film forms silver nanowires-reduction graphite
Alkene composite conductive thin film.
Specifically, the technical matters of the step 32 is identical as the technical matters of step 31.
The production method of flexible transparent conductive film based on above-mentioned first embodiment, the present invention also provides a kind of flexible saturating
Bright conductive film including non-transparent flexible substrate and is attached to several layers of silver nanowires-reduced graphene of non-transparent flexible substrate two sides
Compound/non-reduced method graphene film；The silver nanowires-reduced graphene compound/non-reduced method graphene film
Material includes the silver nanowires-reduced graphene compound and non-reduced method graphene mixed；Described several layers indicate two
Layer or two layers or more；
The silver nanowires-reduced graphene compound includes amination silver nanowires-reduced graphene compound and acetic acid
Change one of silver nanowires-reduced graphene compound or a variety of；
The structural formula of the amination silver nanowires-reduced graphene compound isInstitute
Stating acetoxylation silver nanowires-reduced graphene compound structural formula is
In two above structural formula, the vertical thick line among structural formula indicates silver nanowires, and rGO indicates reduction graphite
Alkene.
Specifically, the non-transparent flexible substrate can be PET (polyethylene terephthalate) film, PI (polyimides)
The transparent flexible films, preferably PET film such as film, PMMA (polymethyl methacrylate) film or PC (polycarbonate) film.
Specifically, the silver nanowires-reduced graphene compound/non-reduced method graphene (AgNWs-rGO/GN) film
In, the non-reduced method graphene (GN) and silver nanowires-reduced graphene compound (AgNWs-rGO) mass ratio are 1:
0.1~500.
Referring to Fig. 3, the second embodiment of the production method for flexible transparent conductive film of the invention, including walk as follows
It is rapid:
Step 10, preparation silver nanowires-reduced graphene (AgNWs-rGO) compound, the silver nanowires-reduction graphite
Alkene compound includes in amination silver nanowires-reduced graphene compound and acetoxylation silver nanowires-reduced graphene compound
It is one or more；
The structural formula of the amination silver nanowires-reduced graphene compound isInstitute
Stating acetoxylation silver nanowires-reduced graphene compound structural formula is
In two above structural formula, the vertical thick line among structural formula indicates silver nanowires, and rGO indicates reduction graphite
Alkene.
The specific embodiment of the step 10 and the production side of technical detail and flexible transparent conductive film of the invention
The step 1 of the first embodiment of method is identical, and details are not described herein again.
Step 20 disperses silver nanowires made from step 10-reduced graphene compound in third organic solvent, obtains
Disperse solution to silver nanowires-reduced graphene compound；By the silver nanowires-reduced graphene compound dispersion solution with
4th organic solvent is uniformly mixed, and obtains silver nanowires-reduced graphene compound (AgNWs-rGO) solution.
Specifically, the third organic solvent dissolves each other with the 4th organic solvent, and the 4th solvent and water are immiscible.
Specifically, the third solvent is acetone；4th solvent is methylene chloride；The silver nanowires-reduction stone
Black alkene compound dispersion solution is mixed with the 4th organic solvent according to the volume ratio of 0.5~5:1.
Specifically, the silver nanowires-reduced graphene complex solution concentration is 0.1-100mg/mL.
Step 30, referring to Fig. 2, provide non-transparent flexible substrate, utilize silver nanowires-reduced graphene made from step 20
Complex solution is respectively formed at least two layers of silver nanowires-in non-transparent flexible substrate two sides by Lang Gemiaoer-Buji spy method and goes back
Former graphene complex film forms silver nanowires-reduced graphene composite conductive thin film.
Specifically, the non-transparent flexible substrate can be PET (polyethylene terephthalate) film, PI (polyimides)
The transparent flexible films, preferably PET film such as film, PMMA (polymethyl methacrylate) film or PC (polycarbonate) film.
Specifically, the step 30 includes:
Step 310 disperses silver nanowires made from step 20-reduced graphene complex solution in water parfacies,
Silver nanowires-reduced graphene complex thin film is formed in water parfacies, and non-transparent flexible substrate is inserted vertically into and is dispersed with silver nanoparticle
In line-reduced graphene complex thin film water parfacies, lifts upwards, the two sides of non-transparent flexible substrate is made to adhere to one layer of silver respectively
Nano wire-reduced graphene complex thin film, obtains the second composite conductive thin film.
Specifically, the step 310 includes: to provide Langmuir-Blodgett film analysis instrument, by silver made from step 20
Nano wire-reduced graphene compound (AgNWs-rGO/GN) solution passes through the sample of Langmuir-Blodgett film analysis instrument
Injection auxiliary system is added drop-wise in the water parfacies in shallow pond, is stood, and silver nanowires-reduced graphene complex thin film is formed, will
Non-transparent flexible substrate, which is suspended on Langmuir-Blodgett film analysis instrument and is inserted vertically into, is dispersed with silver nanowires-reduction stone
It in the water parfacies of black alkene complex thin film, lifts upwards, silver nanowires-reduced graphene complex thin film is attached to transparent flexible
Substrate two sides.
Specifically, the speed that the non-transparent flexible substrate lifts upwards is 1-30mm/min in the step 310.
Step 320 adheres to one layer in the two sides of second composite conductive thin film using Lang Gemiaoer-Buji spy method respectively
Or one layer or more of silver nanowires-reduced graphene complex thin film, it is thin to form silver nanowires-reduced graphene composite conducting
Film.
Specifically, the technical matters of the step 320 is identical as the technical matters of step 310.
Step 40, the non-reduced method graphene (GN) of offer obtain by non-reduced method graphene dispersion in the 5th organic solvent
To non-reduced method graphene solution.
Specifically, the 5th organic solvent and water are immiscible.Preferably, the 5th solvent is chloroform.
Specifically, the non-reduced method graphene is using the graphene of non-oxide reduction method preparation, including useization
Learn one of graphene made from vapor deposition (CVD) method and graphene made from use mechanical stripping method or a variety of.Institute
Stating non-reduced method graphene has layer structure, described to be usually using graphene made from chemical vapor deposition (CVD) method
Single layer structure, described using graphene made from mechanical stripping method is usually multilayered structure.
Specifically, the thickness using graphene made from chemical vapor deposition method is less than 10nm, using mechanical stripping method
Graphene obtained with a thickness of 0.35~35nm.
Specifically, the concentration of the non-reduced method graphene solution is 0.01-10mg/mL.
Step 50, the silver nanowires-reduced graphene composite conductive thin film prepared using step 30 utilize step 40 as substrate
Non-reduced method graphene solution obtained is gone back by special (Langmuir-Blodgett) method of Lang Gemiaoer-Buji in silver nanowires-
Former graphene composite conductive film two sides are respectively formed at least two layers non-reduced method graphene film, and it is thin to obtain flexible and transparent conductive
Film.
Specifically, the step 50 includes:
Step 510 disperses non-reduced method graphene solution made from step 40 in water parfacies, is formed in water parfacies
Silver nanowires-reduced graphene composite conductive thin film is inserted vertically into and is dispersed with non-reduced method stone by non-reduced method graphene film
In the water parfacies of black alkene film, lifts upwards, silver nanowires-reduced graphene composite conductive thin film two sides is made to adhere to one respectively
The non-reduced method graphene film of layer, obtains third composite conductive thin film.
Specifically, the step 510 includes: to provide Langmuir-Blodgett film analysis instrument, it will be non-made from step 40
Reduction method graphene solution is added drop-wise in shallow pond by the sample injection auxiliary system of Langmuir-Blodgett film analysis instrument
In water parfacies, stands, form non-reduced method graphene film, silver nanowires-reduced graphene composite conductive thin film is suspended on
It on Langmuir-Blodgett film analysis instrument and is inserted vertically into the water parfacies for being dispersed with non-reduced method graphene film, upwards
Lifting, non-reduced method graphene film are attached to silver nanowires-reduced graphene composite conductive thin film two sides.
Specifically, in the step 510, speed that the silver nanowires-reduced graphene composite conductive thin film lifts upwards
Degree is 1-30mm/min.
Step 520 adheres to one layer in the two sides of the third composite conductive thin film using Lang Gemiaoer-Buji spy method respectively
Or one layer or more of non-reduced method graphene film, obtain flexible transparent conductive film.
Specifically, the technical matters of the step 520 is identical as the technical matters of step 510.
The production method of flexible transparent conductive film based on above-mentioned second embodiment, the present invention also provides another flexible
Transparent conductive film including non-transparent flexible substrate, is attached respectively to several layers of silver nanowires-of the non-transparent flexible substrate two sides also
Former graphene complex film, several layers of silver nanowires-reduced graphene for being located at the non-transparent flexible substrate two sides are compound
Several layers of non-reduced method graphene film on object film；Described two layers or two layers of several layers of expression or more；
The silver nanowires-reduced graphene compound includes amination silver nanowires-reduced graphene compound and acetic acid
Change one of silver nanowires-reduced graphene compound or a variety of；
The structural formula of the amination silver nanowires-reduced graphene compound isInstitute
Stating acetoxylation silver nanowires-reduced graphene compound structural formula is
In two above structural formula, the vertical thick line among structural formula indicates silver nanowires, and rGO indicates reduction graphite
Alkene.
Specifically, the non-transparent flexible substrate can be PET (polyethylene terephthalate) film, PI (polyimides)
The transparent flexible films, preferably PET film such as film, PMMA (polymethyl methacrylate) film or PC (polycarbonate) film.
In conclusion the present invention provides a kind of flexible transparent conductive film and preparation method thereof.Flexible and transparent of the invention
The production method of conductive film using silver nanowires-reduced graphene compound and non-reduced method graphene as conductive filler,
Flexible transparent conductive film resistant to bending is made using Lang Gemiaoer-Buji spy's method；Silver nanowires-the reduced graphene is compound
Object by obtaining silver nanowires after reduced graphene is modified, go back with non-by the silver nanowires-reduced graphene compound
There are π-π effect between former method graphene, the synergistic effect between conductive filler is improved；Flexible transparent conductive film obtained
Performance be better than existing tin indium oxide conductive film, silver nanowires conductive film, silver nanowires/reduced graphene (AgNWs/
RGO) composite membrane has very excellent mechanical stability and electric conductivity, even across 1500 times or more bendings (0.6 <bending
Radius r < 1.5cm), still it is able to maintain very high conductivity (relative resistance change Δ R/R < 10%).Flexible and transparent of the invention is led
Conductive film uses silver nanowires-reduced graphene compound and non-reduced method graphene as conductive filler, due to silver nanowires-
There are π-π effect between reduced graphene compound and non-reduced method graphene, the synergistic effect between conductive filler is improved,
So that flexible transparent conductive film of the invention has very excellent electric conductivity and mechanical stability.
The above for those of ordinary skill in the art can according to the technique and scheme of the present invention and technology
Other various corresponding changes and modifications are made in design, and all these change and modification all should belong to the claims in the present invention
Protection scope.
Claims (10)
1. a kind of production method of flexible transparent conductive film, which comprises the steps of:
Step 1, preparation silver nanowires-reduced graphene compound, the silver nanowires-reduced graphene compound includes amination
One of silver nanowires-reduced graphene compound and acetoxylation silver nanowires-reduced graphene compound are a variety of；
The structural formula of the amination silver nanowires-reduced graphene compound isThe second
Being acidified silver nanowires-reduced graphene compound structural formula is
In two above structural formula, the vertical thick line among structural formula indicates silver nanowires, and rGO indicates reduced graphene；
Step 2 disperses silver nanowires made from step 1-reduced graphene compound in the first organic solvent, obtains Yin Na
Rice noodles-reduced graphene complex solution；By non-reduced method graphene dispersion in the second organic solvent, non-reduced method stone is obtained
Black alkene solution；Silver nanowires-reduced graphene complex solution is uniformly mixed with non-reduced method graphene solution, obtains Yin Na
Rice noodles-reduced graphene compound/non-reduced method graphene solution；
Step 3 provides non-transparent flexible substrate, utilizes silver nanowires made from step 2-reduced graphene compound/non-reduced method
Graphene solution is respectively formed at least two layers of silver nanowires-in non-transparent flexible substrate two sides by Lang Gemiaoer-Buji spy method and goes back
Former graphene complex/non-reduced method graphene film, obtains flexible transparent conductive film.
2. the production method of flexible transparent conductive film as described in claim 1, which is characterized in that the amination silver nanoparticle
Line-reduced graphene compound preparation method includes the following steps:
Silver nanowires, mercapto-amine, deionized water are added in reaction vessel and are uniformly mixed by step 11, mixed liquor are obtained, to mixing
Liquid carries out centrifugation and removes supernatant, after cleaning lower sediment thing using deionized water, is carried out using deionized water to lower sediment thing
Dispersion, obtains amination silver nanowires aqueous solution；
Graphene oxide powder is added in deionized water step 12, boils and is cooled to 80 DEG C hereinafter, to obtain graphene oxide dense
Contracting liquid；
Step 13, by graphene oxide concentrate made from amination silver nanowires aqueous solution made from step 11 and step 12 48
DEG C~52 DEG C of temperature under the conditions of be mixed 12 hours or more, obtain amination silver nanowires-graphene oxide complex solution；
Reducing agent is added to amination silver nanowires-oxidation in step 14 in amination silver nanowires-graphene oxide complex solution
Graphene complex is restored, and amination silver nanowires-reduced graphene complex solution is obtained；
Step 15 be centrifuged to amination silver nanowires-reduced graphene complex solution and removes supernatant, clear using deionized water
After washing lower sediment thing, amination silver nanowires-reduced graphene compound is obtained；
The sequence of the step 11 and step 12 can be interchanged.
3. the production method of flexible transparent conductive film as described in claim 1, which is characterized in that the acetoxylation silver nanoparticle
Line-reduced graphene compound preparation method includes the following steps:
Step 11 ', will silver nanowires, mercaptoalkyl acid, deionized water be added reaction vessel in be uniformly mixed, obtain mixed liquor,
Centrifugation is carried out to mixed liquor and removes supernatant, after cleaning lower sediment thing using deionized water, lower sediment thing is dried, second is obtained
It is acidified silver nanowires；
Step 12 ', graphene oxide powder and acetoxylation silver nanowires are added in tetrahydrofuran are uniformly dispersed, add 4- bis-
Methylamino pyridine and acid binding agent, 98 DEG C~102 DEG C back flow reaction 12 hours or more, supernatant is removed in centrifugation, using deionized water
After cleaning lower sediment thing, lower sediment thing is dispersed using deionized water, obtains acetoxylation silver nanowires-graphite oxide
Alkene complex solution；
Step 13 ', in acetoxylation silver nanowires-graphene oxide complex solution be added reducing agent to acetoxylation silver nanoparticle
Line-graphene oxide compound is restored, and acetoxylation silver nanowires-reduced graphene complex solution is obtained；
Step 14 ', to acetoxylation silver nanowires-reduced graphene complex solution carry out centrifugation remove supernatant, using deionization
After water cleans lower sediment thing, acetoxylation silver nanowires-reduced graphene compound is obtained.
4. the production method of flexible transparent conductive film as described in claim 1, which is characterized in that the step 3 includes:
Silver nanowires made from step 2-reduced graphene compound/non-reduced method graphene solution is dispersed water by step 31
In parfacies, silver nanowires-reduced graphene compound/non-reduced method graphene film is formed in water parfacies, by transparent flexible
Substrate, which is inserted vertically into, to be dispersed in silver nanowires-reduced graphene compound/non-reduced method graphene film water parfacies, upwards
Lifting, makes the two sides of non-transparent flexible substrate adhere to one layer of silver nanowires-reduced graphene compound/non-reduced method graphene respectively
Film obtains the first composite conductive thin film；
Step 32 adheres to one layer or more in first composite conductive thin film two sides using Lang Gemiaoer-Buji spy method respectively
Silver nanowires-reduced graphene compound/non-reduced method graphene film forms silver nanowires-reduced graphene composite conducting
Film.
5. flexible and transparent conductive made from a kind of production method using flexible transparent conductive film as described in claim 1 is thin
Film, which is characterized in that including non-transparent flexible substrate and be attached to several layers of silver nanowires-reduction graphite of non-transparent flexible substrate two sides
Alkene compound/non-reduced method graphene film；The silver nanowires-reduced graphene compound/non-reduced method graphene film
Material include silver nanowires-reduced graphene compound for mixing and non-reduced method graphene；The several layers of expression
Two layers or more；
The silver nanowires-reduced graphene compound includes amination silver nanowires-reduced graphene compound and acetoxylation silver
One of nano wire-reduced graphene compound is a variety of；
The structural formula of the amination silver nanowires-reduced graphene compound isThe second
Being acidified silver nanowires-reduced graphene compound structural formula is
In two above structural formula, the vertical thick line among structural formula indicates silver nanowires, and rGO indicates reduced graphene.
6. a kind of production method of flexible transparent conductive film, which comprises the steps of:
Step 10, preparation silver nanowires-reduced graphene compound, the silver nanowires-reduced graphene compound includes amine
Change one of silver nanowires-reduced graphene compound and acetoxylation silver nanowires-reduced graphene compound or a variety of；
The structural formula of the amination silver nanowires-reduced graphene compound isThe second
Being acidified silver nanowires-reduced graphene compound structural formula is
In two above structural formula, the vertical thick line among structural formula indicates silver nanowires, and rGO indicates reduced graphene；
Step 20 disperses silver nanowires made from step 10-reduced graphene compound in third organic solvent, obtains silver
Nano wire-reduced graphene compound disperses solution；The silver nanowires-reduced graphene compound is dispersed into solution and the 4th
Organic solvent is uniformly mixed, and obtains silver nanowires-reduced graphene complex solution；
Step 30 provides non-transparent flexible substrate, is passed through using silver nanowires made from step 20-reduced graphene complex solution
Lang Gemiaoer-Buji spy method is respectively formed at least two layers silver nanowires-reduced graphene compound in non-transparent flexible substrate two sides
Film forms silver nanowires-reduced graphene composite conductive thin film；
Step 40, the non-reduced method graphene of offer obtain non-reduced by non-reduced method graphene dispersion in the 5th organic solvent
Method graphene solution；
Step 50, the silver nanowires-reduced graphene composite conductive thin film prepared using step 30 are made as substrate using step 40
Non-reduced method graphene solution by Lang Gemiaoer-Buji spy method in silver nanowires-reduced graphene composite conductive thin film two
Side is respectively formed at least two layers non-reduced method graphene film, obtains flexible transparent conductive film.
7. the production method of flexible transparent conductive film as claimed in claim 6, which is characterized in that the amination silver nanoparticle
Line-reduced graphene compound preparation method includes the following steps:
Silver nanowires, mercapto-amine, deionized water are added in reaction vessel and are uniformly mixed by step 11, mixed liquor are obtained, to mixing
Liquid carries out centrifugation and removes supernatant, after cleaning lower sediment thing using deionized water, is carried out using deionized water to lower sediment thing
Dispersion, obtains amination silver nanowires aqueous solution；
Graphene oxide powder is added in deionized water step 12, boils and is cooled to 80 DEG C hereinafter, to obtain graphene oxide dense
Contracting liquid；
Step 13, by graphene oxide concentrate made from amination silver nanowires aqueous solution made from step 11 and step 12 48
DEG C~52 DEG C of temperature under the conditions of be mixed 12 hours or more, obtain amination silver nanowires-graphene oxide complex solution；
Reducing agent is added to amination silver nanowires-oxidation in step 14 in amination silver nanowires-graphene oxide complex solution
Graphene complex is restored, and amination silver nanowires-reduced graphene complex solution is obtained；
Step 15 be centrifuged to amination silver nanowires-reduced graphene complex solution and removes supernatant, clear using deionized water
After washing lower sediment thing, amination silver nanowires-reduced graphene compound is obtained.
8. the production method of flexible transparent conductive film as claimed in claim 6, which is characterized in that the acetoxylation silver nanoparticle
Line-reduced graphene compound preparation method includes the following steps:
Step 11 ', will silver nanowires, mercaptoalkyl acid, deionized water be added reaction vessel in be uniformly mixed, obtain mixed liquor,
Centrifugation is carried out to mixed liquor and removes supernatant, after cleaning lower sediment thing using deionized water, lower sediment thing is dried, second is obtained
It is acidified silver nanowires；
Step 12 ', graphene oxide powder and acetoxylation silver nanowires are added in tetrahydrofuran are uniformly dispersed, add 4- bis-
Methylamino pyridine and acid binding agent, 98 DEG C~102 DEG C back flow reaction 12 hours or more, supernatant is removed in centrifugation, using deionized water
After cleaning lower sediment thing, lower sediment thing is dispersed using deionized water, obtains acetoxylation silver nanowires-graphite oxide
Alkene complex solution；
Step 13 ', in acetoxylation silver nanowires-graphene oxide complex solution be added reducing agent to acetoxylation silver nanoparticle
Line-graphene oxide compound is restored, and acetoxylation silver nanowires-reduced graphene complex solution is obtained；
Step 14 ', to acetoxylation silver nanowires-reduced graphene complex solution carry out centrifugation remove supernatant, using deionization
After water cleans lower sediment thing, acetoxylation silver nanowires-reduced graphene compound is obtained.
9. the production method of flexible transparent conductive film as claimed in claim 6, which is characterized in that the step 30 includes:
Step 310 disperses silver nanowires made from step 20-reduced graphene complex solution in water parfacies, in water Asia
Silver nanowires-reduced graphene complex thin film is formed in phase, and non-transparent flexible substrate is inserted vertically into and is dispersed with silver nanowires-also
In the water parfacies of former graphene complex film, lifts upwards, the two sides of non-transparent flexible substrate is made to adhere to one layer of silver nanoparticle respectively
Line-reduced graphene complex thin film, obtains the second composite conductive thin film；
Step 320 adheres to one layer or more in the two sides of second composite conductive thin film using Lang Gemiaoer-Buji spy method respectively
Silver nanowires-reduced graphene complex thin film, formed silver nanowires-reduced graphene composite conductive thin film；
The step 50 includes:
Step 510 disperses non-reduced method graphene solution made from step 40 in water parfacies, and non-go back is formed in water parfacies
Silver nanowires-reduced graphene composite conductive thin film is inserted vertically into and is dispersed with non-reduced method graphene by former method graphene film
In the water parfacies of film, upwards lift, make silver nanowires-reduced graphene composite conductive thin film two sides adhere to respectively one layer it is non-
Reduction method graphene film obtains third composite conductive thin film；
Step 520 adheres to one layer or more in the two sides of the third composite conductive thin film using Lang Gemiaoer-Buji spy method respectively
Non-reduced method graphene film, obtain flexible transparent conductive film.
10. flexible and transparent conductive made from a kind of production method using flexible transparent conductive film as claimed in claim 6
Film, which is characterized in that including non-transparent flexible substrate, be attached respectively to several layers of silver nanoparticle of the non-transparent flexible substrate two sides
Line-reduced graphene complex thin film, several layers of silver nanowires-reduced graphene for being located at the non-transparent flexible substrate two sides
Several layers of non-reduced method graphene film on complex thin film；Described two layers of several layers of expression or more；
The silver nanowires-reduced graphene compound includes amination silver nanowires-reduced graphene compound and acetoxylation silver
One of nano wire-reduced graphene compound is a variety of；
The structural formula of the amination silver nanowires-reduced graphene compound isThe second
Being acidified silver nanowires-reduced graphene compound structural formula is
In two above structural formula, the vertical thick line among structural formula indicates silver nanowires, and rGO indicates reduced graphene.
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