CN108751179A - A kind of preparation method of transparent graphene conductive film - Google Patents
A kind of preparation method of transparent graphene conductive film Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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- H—ELECTRICITY
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Abstract
The invention discloses a kind of preparation methods of transparent graphene conductive film, belong to conductive material technical field.Carbon dioxide is passed through with the rate of 20~30mL/min into polyallylamine mixture, is 40~45 DEG C in temperature, under conditions of rotating speed is 250~300r/min, after being stirred 20~30min, obtains mixture；By mixture and hydrazine hydrate in mass ratio 8：1~10：1 mixing under conditions of frequency is 55~65kHz after 15~20min of ultrasonic disperse, is 45~55 DEG C in temperature, under conditions of rotating speed is 380~450r/min, after being stirred to react 2~4h, obtains blank liquid；Blank liquid is filtered by vacuum, transparent graphene conductive film blank is obtained, under conditions of being 65~75 DEG C in temperature by transparent graphene conductive film blank after dry 2~3h, obtains transparent graphene conductive film.Gained transparent graphene conductive film of the invention has excellent electric conductivity.
Description
Technical field
The invention discloses a kind of preparation methods of transparent graphene conductive film, belong to conductive material technical field.
Background technology
Conducting polymer can be divided into structural type by composition and electrical conduction mechanism（Intrinsical）With it is compound（Doping type）.It is compound
Conducting polymer by the clear superiority of electric conductivity, stability, processability etc., be increasingly becoming research enliven, quickly grow,
Widely used one kind conductive material.It is to be added to conductive filler to realize conduction in nonconducting macromolecule matrix,
Its electrical conduction mechanism is generally acknowledged that the conductive filler in matrix contacts with each other to form continuous conductive network, and carrier can be in a network
Movement, to keep graphene oxide composite conductive film conductive.Common conductive filler mainly has carbon filler, metal packing, metal
Oxide filler and compounded mix.Carbon filler has that at low cost, raw material is easy to get, density is small, property is stable, environmental-friendly etc. excellent
Point, upper in the selection and use of conductive filler, proportion increasingly increases.
Transparent conductive film（TCF）It is the important component of the photoelectric devices such as touch screen, display, solar cell.
Nowadays, tin indium oxide（ITO）It is widely used on these photoelectric devices, but tin indium oxide lacks flexibility, it is difficult to deposit
On flexible substrates, it is difficult to meet the requirement in epoch.In this regard, people have attempted many other materials to substitute ITO, such as：Carbon is received
Mitron, conducting polymer, silver（Or copper）Nano wire etc., but respectively have advantage and disadvantage.For noble metal nano wire, nano wire it is pure
Degree and radius size and draw ratio largely affect the performance of the transparency conducting layer based on nano wire.Except this it
Outside, since that there are matter is crisp, is unlikely to deform for photovoltaic substrate, the application of transparent conductive film is limited.With hard substrate electrically conducting transparent
Film is compared, the transparent conductive film prepared on organic flexible base material not only photoelectric characteristic having the same, but also with being permitted
More particular advantages, such as：It is flexible, light-weight, non-breakable, roll-to-roll industrialization continuous production mode may be used be conducive to carry
High efficiency is readily transported.The problem of conductive film traditional at present can not be further increased there is also electric conductivity, therefore also need
It is studied.
Invention content
The present invention solves the technical problem of：It is bad for conventional graphite alkene conductive film transparency, electric conductivity without
The problem of method is further promoted provides a kind of preparation method of transparent graphene conductive film.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
（1）By graphene oxide and water in mass ratio 1：200~1：300 mix, and after ultrasonic disperse, graphene oxide quality is added
0.3~0.5 aminating agent after being stirred to react, obtains amination graphene oxide mixture；
（2）By polyallylamine hydrochlorides and water in mass ratio 1：100~1：150 mixing, adjust pH to 9.8~10.0, obtain polyene
Propylamin hydrochloride solution is passed through nitrogen into polyallylamine hydrochlorides solution, and under conditions of being vigorously stirred, to polyallylamine
HCI solution instills the modification of chitosan mixture of 1.0~1.5 times of polyallylamine hydrochlorides solution quality, after being stirred to react,
Pretreatment additive blank is obtained, by pretreatment additive blank and sodium borohydride in mass ratio 20：1~30：1 mixing, in nitrogen
After being stirred under atmosphere, additive blank is obtained, after additive blank is dialysed, obtains additive；
（3）By amination graphene oxide mixture and silver ammino solution in mass ratio 5：1~10：1 mixing, and amination oxygen is added
0.2~0.3 times of the additive of 0.1~0.2 times of graphite alkene mixture quality and amination graphene oxide mixture quality
Polyallylamine after being stirred, obtains polyallylamine mixture；
（4）It is passed through carbon dioxide into polyallylamine mixture, after being stirred, obtains mixture；Mixture and hydrazine hydrate are pressed
Mass ratio 8：1~10：1 mixes, and after ultrasonic disperse, is stirred to react, obtains blank liquid；
（5）Blank liquid is filtered by vacuum, transparent graphene conductive film blank is obtained, transparent graphene conductive film blank is dried, is obtained
Transparent graphene conductive film.
Step（1）The aminating agent is ethylenediamine, any one in triethylene tetramine or diethylenetriamine.
Step（2）The modification of chitosan mixture is by glucose and water in mass ratio 1：20~1：25 mixing, and add
The Potassiumiodate for entering 0.1~0.2 times of glucose quality after being stirred, obtains glucose mixed liquor, by glucose mixed liquor and chlorination
Barium solution in mass ratio 1：3~1：5 mixing, filtering obtain filtrate, by filtrate and metabisulfite solution in mass ratio 1：3~1：4 is mixed
It closes, filtering removes filter cake, obtains modified glucose mixture.
Step（3）The silver ammino solution is by silver nitrate and water in mass ratio 1：10~1：30 mixing, and ammonium hydroxide is added dropwise extremely
Precipitation all disappears, and obtains silver ammino solution.
The beneficial effects of the invention are as follows：
（1）Additive is added when preparing transparent graphene conductive film in the present invention, first, microgel structure is contained in additive
Active ingredient can be after amino group graphene be reduced after being added in product, and the amination graphene of formation is due to pi-pi bond
During autohemagglutination occurs, into the interlayer structure of amination graphene, to reduce the autohemagglutination phenomenon of amination graphene, make production
The number of plies of product amination graphene in preparation process is reduced, and since active ingredient is transparent, to make the transparency of product carry
It is high；Secondly as the active ingredient of microgel structure is sensitive to pH, and in product preparation process, as silver ammino solution is reduced,
The ammonia of generation is partially soluble in water, and the pH of system is made to increase, and to make active ingredient expand, and then adsorbs the nano silver generated
Particle is brought nano-Ag particles into the interlayer structure of amination graphene, and the electric conductivity of product is made to improve；
（2）Silver ammino solution and polyallylamine are added when preparing transparent graphene conductive film by the present invention, on the one hand, the polyene of addition
Propylamine can crosslink under the action of carbon dioxide with the polyallylamine hydrochlorides in additive, be handed over to be formed in system
Networking network, amination graphene oxide is fixed in network structure, and then avoid amination graphene oxide in reduction process
In quick reunion, improve the transparency of product, on the other hand, the silver ammino solution of addition can be hydrated in product preparation process
Hydrazine restores, and forms nano-Ag particles, ammonia and nitrogen, the ammonia of formation are partially soluble in water, improve the pH of system, make additive
In active ingredient expansion, and formed nitrogen can make under carbon dioxide formed cross-linked network polyallylamine and polyallylamine
Hydrochloride solution is crosslinked, and to generate carbon dioxide, also, with crosslinked progress is solved, amination graphene oxide is gradually gone back
Original is concurrently born from poly- at amination graphene, and the nano silver of generation can be fixed between amination graphene layer while autohemagglutination and tied
In structure, the reunion of nano-Ag particles is not only reduced, improves the dispersibility of nano silver, and reduce amination graphite to a certain extent
The reunion of alkene, and then the electric conductivity of product is made to improve.
Specific implementation mode
By glucose and water in mass ratio 1：20~1：25 are mixed in beaker, and glucose quality is added into beaker
0.1~0.2 times of Potassiumiodate is 30~45 DEG C in temperature, under conditions of rotating speed is 300~400r/min, it is stirred 40~
After 60min, obtain glucose mixed liquor, by glucose mixed liquor and mass fraction be 12~18% barium chloride solution in mass ratio
1：3~1：5 mixing are 30~45 DEG C in temperature, under conditions of rotating speed is 250~400r/min, are stirred 30~50min
Afterwards, it filters, obtains filtrate, the metabisulfite solution in mass ratio 1 for being 15~20% by filtrate and mass fraction：3~1：4 mixing, Yu Wen
Degree is 30~45 DEG C, and under conditions of rotating speed is 250~400r/min, after being stirred 35~45min, filtering removes filter cake, obtains
Modified glucose mixture；By graphene oxide and water in mass ratio 1：200~1：300 mixing, in frequency be 45~65kHz
Under the conditions of, after 20~30min of ultrasonic disperse, and graphene oxide quality 0.3 is added into the mixture of graphene oxide and water
~0.5 aminating agent is 45~60 DEG C in temperature, under conditions of rotating speed is 300~350r/min, after being stirred to react 8~10h, obtains
Amination graphene oxide mixture；By polyallylamine hydrochlorides and water in mass ratio 1：100~1：150 mix, and are in temperature
45~55 DEG C, be 10~15% with mass fraction after being stirred 30~40min under conditions of rotating speed is 300~400r/min
Sodium hydroxide solution adjust polyallylamine hydrochlorides and aqueous mixtures pH to 9.8~10.0, it is molten to obtain polyallylamine hydrochlorides
Liquid is passed through nitrogen into polyallylamine hydrochlorides solution with the rate of 20~30mL/min, in rotating speed be 800~1200r/min
Under conditions of, polyallylamine hydrochlorides solution quality 1.0 is instilled to polyallylamine hydrochlorides solution with the rate of 5~10mL/min
~1.5 times of modification of chitosan mixture is 30~40 DEG C in temperature, and under conditions of rotating speed is 300~400r/min, stirring is anti-
After answering 2~4h, pretreatment additive blank is obtained, by pretreatment additive blank and sodium borohydride in mass ratio 20：1~30：1 is mixed
Together in three-necked flask, and nitrogen is passed through with the rate of 10~30mL/min into three-necked flask, is 45~65 DEG C in temperature, turns
Under conditions of speed is 300~380r/min, after being stirred to react 10~12h, additive blank is obtained, by the retention point of additive blank
The bag filter of son amount 10000 is dialysed after 10~20h, and additive is obtained；Amination graphene oxide mixture is pressed with silver ammino solution
Mass ratio 5：1~10：1 is mixed in four-hole boiling flask, and amination graphene oxide mixture quality is added into four-hole boiling flask
The polyallylamine of 0.1~0.2 times of 0.2~0.3 times of additive and amination graphene oxide mixture quality, in temperature be 45
~55 DEG C, under conditions of rotating speed is 300~500r/min, after being stirred 30~50min, obtain polyallylamine mixture；Xiang Ju
Carbon dioxide is passed through with the rate of 20~30mL/min in allyl amine blends, in temperature be 40~45 DEG C, rotating speed be 250~
Under conditions of 300r/min, after being stirred 20~30min, mixture is obtained；By mixture and hydrazine hydrate in mass ratio 8：1~
10：1 mixing is 45~55 DEG C in temperature, rotating speed is under conditions of frequency is 55~65kHz after 15~20min of ultrasonic disperse
Under conditions of 380~450r/min, after being stirred to react 2~4h, blank liquid is obtained；Blank liquid is filtered by vacuum, transparent graphene is obtained
Conductive film blank obtains transparent stone under conditions of being 65~75 DEG C in temperature by transparent graphene conductive film blank after dry 2~3h
Black alkene conductive film.The aminating agent is ethylenediamine, any one in triethylene tetramine or diethylenetriamine.The silver ammino solution is
By silver nitrate and water in mass ratio 1：10~1：30 mixing, and the ammonium hydroxide that mass fraction is 15~20% is added dropwise and all disappears to precipitation
It loses, obtains silver ammino solution.
By glucose and water in mass ratio 1：25 are mixed in beaker, and 0.2 times of glucose quality is added into beaker
Potassiumiodate is 45 DEG C in temperature, under conditions of rotating speed is 400r/min, after being stirred 60min, obtains glucose mixed liquor, will
The barium chloride solution in mass ratio 1 that glucose mixed liquor is 18% with mass fraction：5 mixing are 45 DEG C in temperature, and rotating speed is
Under conditions of 400r/min, after being stirred 50min, filtering obtains filtrate, and filtrate is molten for 20% sodium sulphate with mass fraction
Liquid in mass ratio 1：4 mixing are 45 DEG C in temperature, and under conditions of rotating speed is 400r/min, after being stirred 45min, filtering is gone
Except filter cake, modified glucose mixture is obtained；By graphene oxide and water in mass ratio 1：300 mixing, in the item that frequency is 65kHz
Under part, after ultrasonic disperse 30min, and 0.5 aminating agent of graphene oxide quality is added into the mixture of graphene oxide and water,
It is 60 DEG C in temperature, under conditions of rotating speed is 350r/min, after being stirred to react 10h, obtains amination graphene oxide mixture；It will
Polyallylamine hydrochlorides and water in mass ratio 1：150 mixing are 55 DEG C in temperature, under conditions of rotating speed is 400r/min, stir
After mixing 40min, the sodium hydroxide solution for being 15% with mass fraction adjust the pH of polyallylamine hydrochlorides and aqueous mixtures to
10.0, obtain polyallylamine hydrochlorides solution, nitrogen be passed through with the rate of 30mL/min into polyallylamine hydrochlorides solution, in turn
Under conditions of speed is 1200r/min, polyallylamine hydrochlorides are instilled to polyallylamine hydrochlorides solution with the rate of 10mL/min
The modification of chitosan mixture of 1.5 times of solution quality is 40 DEG C in temperature, under conditions of rotating speed is 400r/min, is stirred to react
After 4h, pretreatment additive blank is obtained, by pretreatment additive blank and sodium borohydride in mass ratio 30：1 is mixed in three mouthfuls of burnings
In bottle, and nitrogen is passed through with the rate of 30mL/min into three-necked flask, is 65 DEG C in temperature, rotating speed is the condition of 380r/min
Under, after being stirred to react 12h, additive blank is obtained, after the bag filter dialysis 20h of additive blank molecular cut off 10000,
Obtain additive；By amination graphene oxide mixture and silver ammino solution in mass ratio 10：1 is mixed in four-hole boiling flask, and to
The additive and amination graphene oxide mixture of 0.2 times of amination graphene oxide mixture quality are added in four-hole boiling flask
The polyallylamine that 0.3 times of quality is 55 DEG C in temperature, under conditions of rotating speed is 500r/min, after being stirred 50min, obtains poly-
Allyl amine blends；Carbon dioxide is passed through with the rate of 30mL/min into polyallylamine mixture, in temperature be 45 DEG C, rotating speed
Under conditions of 300r/min, after being stirred 30min, mixture is obtained；By mixture and hydrazine hydrate in mass ratio 10：1 mixing,
Under conditions of frequency is 65kHz after ultrasonic disperse 20min, it is 55 DEG C in temperature, under conditions of rotating speed is 450r/min, stirs
After reacting 4h, blank liquid is obtained；Blank liquid is filtered by vacuum, transparent graphene conductive film blank is obtained, by transparent graphene conductive film
Under conditions of blank is 75 DEG C in temperature after dry 3h, transparent graphene conductive film is obtained.The aminating agent is ethylenediamine.The silver
Ammonia solution is by silver nitrate and water in mass ratio 1：30 mixing, and the ammonium hydroxide that mass fraction is 20% is added dropwise and all disappears to precipitation,
Obtain silver ammino solution.
By glucose and water in mass ratio 1：25 are mixed in beaker, and 0.2 times of glucose quality is added into beaker
Potassiumiodate is 45 DEG C in temperature, under conditions of rotating speed is 400r/min, after being stirred 60min, obtains glucose mixed liquor, will
The barium chloride solution in mass ratio 1 that glucose mixed liquor is 18% with mass fraction：5 mixing are 45 DEG C in temperature, and rotating speed is
Under conditions of 400r/min, after being stirred 50min, filtering obtains filtrate, and filtrate is molten for 20% sodium sulphate with mass fraction
Liquid in mass ratio 1：4 mixing are 45 DEG C in temperature, and under conditions of rotating speed is 400r/min, after being stirred 45min, filtering is gone
Except filter cake, modified glucose mixture is obtained；By graphene oxide and water in mass ratio 1：300 mixing, in the item that frequency is 65kHz
Under part, after ultrasonic disperse 30min, and 0.5 aminating agent of graphene oxide quality is added into the mixture of graphene oxide and water,
It is 60 DEG C in temperature, under conditions of rotating speed is 350r/min, after being stirred to react 10h, obtains amination graphene oxide mixture；It will
Amination graphene oxide mixture and silver ammino solution in mass ratio 10：1 is mixed in four-hole boiling flask, and adds into four-hole boiling flask
The polyallylamine for entering 0.3 times of amination graphene oxide mixture quality is 55 DEG C in temperature, and rotating speed is the condition of 500r/min
Under, after being stirred 50min, obtain polyallylamine mixture；Into polyallylamine mixture two are passed through with the rate of 30mL/min
Carbonoxide is 45 DEG C in temperature, under conditions of rotating speed is 300r/min, after being stirred 30min, obtains mixture；By mixture
With hydrazine hydrate in mass ratio 10：1 mixing under conditions of frequency is 65kHz after ultrasonic disperse 20min, is 55 DEG C in temperature, turns
Under conditions of speed is 450r/min, after being stirred to react 4h, blank liquid is obtained；Blank liquid is filtered by vacuum, transparent graphene conduction is obtained
Film blank obtains transparent graphene conductive film under conditions of being 75 DEG C in temperature by transparent graphene conductive film blank after dry 3h.
The aminating agent is ethylenediamine.The silver ammino solution is by silver nitrate and water in mass ratio 1：30 mixing, and mass fraction is added dropwise
The ammonium hydroxide for being 20% obtains silver ammino solution to whole disappearances are precipitated.
By glucose and water in mass ratio 1：25 are mixed in beaker, and 0.2 times of glucose quality is added into beaker
Potassiumiodate is 45 DEG C in temperature, under conditions of rotating speed is 400r/min, after being stirred 60min, obtains glucose mixed liquor, will
The barium chloride solution in mass ratio 1 that glucose mixed liquor is 18% with mass fraction：5 mixing are 45 DEG C in temperature, and rotating speed is
Under conditions of 400r/min, after being stirred 50min, filtering obtains filtrate, and filtrate is molten for 20% sodium sulphate with mass fraction
Liquid in mass ratio 1：4 mixing are 45 DEG C in temperature, and under conditions of rotating speed is 400r/min, after being stirred 45min, filtering is gone
Except filter cake, modified glucose mixture is obtained；By graphene oxide and water in mass ratio 1：300 mixing, in the item that frequency is 65kHz
Under part, after ultrasonic disperse 30min, and 0.5 aminating agent of graphene oxide quality is added into the mixture of graphene oxide and water,
It is 60 DEG C in temperature, under conditions of rotating speed is 350r/min, after being stirred to react 10h, obtains amination graphene oxide mixture；It will
Polyallylamine hydrochlorides and water in mass ratio 1：150 mixing are 55 DEG C in temperature, under conditions of rotating speed is 400r/min, stir
After mixing 40min, the sodium hydroxide solution for being 15% with mass fraction adjust the pH of polyallylamine hydrochlorides and aqueous mixtures to
10.0, obtain polyallylamine hydrochlorides solution, nitrogen be passed through with the rate of 30mL/min into polyallylamine hydrochlorides solution, in turn
Under conditions of speed is 1200r/min, polyallylamine hydrochlorides are instilled to polyallylamine hydrochlorides solution with the rate of 10mL/min
The modification of chitosan mixture of 1.5 times of solution quality is 40 DEG C in temperature, under conditions of rotating speed is 400r/min, is stirred to react
After 4h, pretreatment additive blank is obtained, by pretreatment additive blank and sodium borohydride in mass ratio 30：1 is mixed in three mouthfuls of burnings
In bottle, and nitrogen is passed through with the rate of 30mL/min into three-necked flask, is 65 DEG C in temperature, rotating speed is the condition of 380r/min
Under, after being stirred to react 12h, additive blank is obtained, after the bag filter dialysis 20h of additive blank molecular cut off 10000,
Obtain additive；Amination graphene oxide mixture is added in four-hole boiling flask, and amination oxidation is added into four-hole boiling flask
The polyallylamine of 0.3 times of the additive and amination graphene oxide mixture quality that 0.2 times of graphene mixture quality, Yu Wen
Degree is 55 DEG C, under conditions of rotating speed is 500r/min, after being stirred 50min, obtains polyallylamine mixture；It is mixed to polyallylamine
It closes in object and carbon dioxide is passed through with the rate of 30mL/min, be 45 DEG C in temperature, under conditions of rotating speed is 300r/min, stirring is mixed
After closing 30min, mixture is obtained；By mixture and hydrazine hydrate in mass ratio 10：1 mixing, the ultrasound under conditions of frequency is 65kHz
After disperseing 20min, it is 55 DEG C in temperature, under conditions of rotating speed is 450r/min, after being stirred to react 4h, obtains blank liquid；By blank
Liquid is filtered by vacuum, and obtains transparent graphene conductive film blank, by transparent graphene conductive film blank under conditions of temperature is 75 DEG C
After dry 3h, transparent graphene conductive film is obtained.The aminating agent is ethylenediamine.The silver ammino solution is that silver nitrate and water are pressed matter
Measure ratio 1：30 mixing, and the ammonium hydroxide that mass fraction is 20% is added dropwise and all disappears to precipitation, obtain silver ammino solution.
By glucose and water in mass ratio 1：25 are mixed in beaker, and 0.2 times of glucose quality is added into beaker
Potassiumiodate is 45 DEG C in temperature, under conditions of rotating speed is 400r/min, after being stirred 60min, obtains glucose mixed liquor, will
The barium chloride solution in mass ratio 1 that glucose mixed liquor is 18% with mass fraction：5 mixing are 45 DEG C in temperature, and rotating speed is
Under conditions of 400r/min, after being stirred 50min, filtering obtains filtrate, and filtrate is molten for 20% sodium sulphate with mass fraction
Liquid in mass ratio 1：4 mixing are 45 DEG C in temperature, and under conditions of rotating speed is 400r/min, after being stirred 45min, filtering is gone
Except filter cake, modified glucose mixture is obtained；By graphene oxide and water in mass ratio 1：300 mixing, in the item that frequency is 65kHz
Under part, after ultrasonic disperse 30min, and 0.5 aminating agent of graphene oxide quality is added into the mixture of graphene oxide and water,
It is 60 DEG C in temperature, under conditions of rotating speed is 350r/min, after being stirred to react 10h, obtains amination graphene oxide mixture；It will
Polyallylamine hydrochlorides and water in mass ratio 1：150 mixing are 55 DEG C in temperature, under conditions of rotating speed is 400r/min, stir
After mixing 40min, the sodium hydroxide solution for being 15% with mass fraction adjust the pH of polyallylamine hydrochlorides and aqueous mixtures to
10.0, obtain polyallylamine hydrochlorides solution, nitrogen be passed through with the rate of 30mL/min into polyallylamine hydrochlorides solution, in turn
Under conditions of speed is 1200r/min, polyallylamine hydrochlorides are instilled to polyallylamine hydrochlorides solution with the rate of 10mL/min
The modification of chitosan mixture of 1.5 times of solution quality is 40 DEG C in temperature, under conditions of rotating speed is 400r/min, is stirred to react
After 4h, pretreatment additive blank is obtained, by pretreatment additive blank and sodium borohydride in mass ratio 30：1 is mixed in three mouthfuls of burnings
In bottle, and nitrogen is passed through with the rate of 30mL/min into three-necked flask, is 65 DEG C in temperature, rotating speed is the condition of 380r/min
Under, after being stirred to react 12h, additive blank is obtained, after the bag filter dialysis 20h of additive blank molecular cut off 10000,
Obtain additive；By amination graphene oxide mixture and silver ammino solution in mass ratio 10：1 is mixed in four-hole boiling flask, and to
The additive of 0.2 times of amination graphene oxide mixture quality is added in four-hole boiling flask, is 55 DEG C in temperature, rotating speed is
Under conditions of 500r/min, after being stirred 50min, mixture is obtained；Dioxy is passed through with the rate of 30mL/min into mixture
Change carbon, is 45 DEG C in temperature, under conditions of rotating speed is 300r/min, after being stirred 30min, obtains mixture；By mixture with
Hydrazine hydrate in mass ratio 10：1 mixing, under conditions of frequency is 65kHz after ultrasonic disperse 20min, in temperature be 55 DEG C, rotating speed
Under conditions of 450r/min, after being stirred to react 4h, blank liquid is obtained；Blank liquid is filtered by vacuum, transparent graphene conductive film is obtained
Blank obtains transparent graphene conductive film under conditions of being 75 DEG C in temperature by transparent graphene conductive film blank after dry 3h.Institute
It is ethylenediamine to state aminating agent.The silver ammino solution is by silver nitrate and water in mass ratio 1：30 mixing, and mass fraction is added dropwise and is
20% ammonium hydroxide obtains silver ammino solution to all disappearances are precipitated.
Comparative example：The grapheme conductive film of Changzhou Science and Technology Ltd. production.
1 to 4 gained grapheme conductive film of example and comparative example product are subjected to performance detection, specific detection method is as follows：
UV-Vis tests are carried out to the translucency of above-mentioned conductive film, with the surface resistance of the above-mentioned conductive film of four-point probe measurment.
Specific testing result is as shown in table 1：
Table 1：Performance detection table
| Detection project | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Square resistance/Ω | 20.3 | 29.4 | 30.1 | 28.5 | 42.7 |
| Translucency/% | 90.6 | 83.3 | 85.3 | 84.8 | 74.6 |
By 1 testing result of table it is found that present invention gained transparent graphene conductive film has excellent electric conductivity.
Claims (4)
1. a kind of preparation method of transparent graphene conductive film, which is characterized in that specifically preparation method is：
（1）By graphene oxide and water in mass ratio 1：200~1：300 mix, and after ultrasonic disperse, graphene oxide quality is added
0.3~0.5 aminating agent after being stirred to react, obtains amination graphene oxide mixture；
（2）By polyallylamine hydrochlorides and water in mass ratio 1：100~1：150 mixing, adjust pH to 9.8~10.0, obtain polyene
Propylamin hydrochloride solution is passed through nitrogen into polyallylamine hydrochlorides solution, and under conditions of being vigorously stirred, to polyallylamine
HCI solution instills the modification of chitosan mixture of 1.0~1.5 times of polyallylamine hydrochlorides solution quality, after being stirred to react,
Pretreatment additive blank is obtained, by pretreatment additive blank and sodium borohydride in mass ratio 20：1~30：1 mixing, in nitrogen
After being stirred under atmosphere, additive blank is obtained, after additive blank is dialysed, obtains additive；
（3）By amination graphene oxide mixture and silver ammino solution in mass ratio 5：1~10：1 mixing, and amination oxygen is added
0.2~0.3 times of the additive of 0.1~0.2 times of graphite alkene mixture quality and amination graphene oxide mixture quality
Polyallylamine after being stirred, obtains polyallylamine mixture；
（4）It is passed through carbon dioxide into polyallylamine mixture, after being stirred, obtains mixture；Mixture and hydrazine hydrate are pressed
Mass ratio 8：1~10：1 mixes, and after ultrasonic disperse, is stirred to react, obtains blank liquid；
（5）Blank liquid is filtered by vacuum, transparent graphene conductive film blank is obtained, transparent graphene conductive film blank is dried, is obtained
Transparent graphene conductive film.
2. a kind of preparation method of transparent graphene conductive film according to claim 1, it is characterised in that：Step（1）Institute
It is ethylenediamine to state aminating agent, any one in triethylene tetramine or diethylenetriamine.
3. a kind of preparation method of transparent graphene conductive film according to claim 1, it is characterised in that：Step（2）Institute
It is by glucose and water in mass ratio 1 to state modification of chitosan mixture：20~1：25 mixing, and be added glucose quality 0.1~
0.2 times of Potassiumiodate after being stirred, obtains glucose mixed liquor, by glucose mixed liquor and barium chloride solution in mass ratio 1：3
~1：5 mixing, filtering obtain filtrate, by filtrate and metabisulfite solution in mass ratio 1：3~1：4 mixing, filtering remove filter cake, obtain
Modified glucose mixture.
4. a kind of preparation method of transparent graphene conductive film according to claim 1, it is characterised in that：Step（3）Institute
It is by silver nitrate and water in mass ratio 1 to state silver ammino solution：10~1：30 mixing, and ammonium hydroxide is added dropwise to all disappearances are precipitated, it obtains silver-colored
Ammonia solution.
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