CN104882223A - Oxidized graphene/silver nanowire composite transparent conducting thin film and preparation method thereof - Google Patents
Oxidized graphene/silver nanowire composite transparent conducting thin film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of an oxidized graphene/silver nanowire composite transparent conducting thin film. The method includes the steps of: (1) providing a substrate; (2) coating silver nanowires on the substrate to obtain a silver nanowire conducting layer; and (3) continuing to coat oxidized graphene on the silver nanowire conducting layer to obtain an oxidized graphene layer. The oxidized graphene/silver nanowire composite transparent conducting thin film provided by the invention has strong adhesive force to the substrate, high oxidation resistance and good conductivity, is simple in preparation technology and low in cost.
Description
Technical field
The present invention relates to electric conducting material preparation field, particularly relate to a kind of graphene oxide/nano silver wire compound transparent electricity conductive film and preparation method thereof.
Background technology
Transparent conducting coating is the important composition part of a lot of electronic device (transparency electrode as in liquid crystal display, Organic Light Emitting Diode, flexible display and Electronic Paper, solar cell).Transparent conductive material in the market mainly contains indium tin oxide (ITO), antimony tin oxide (ATO), antimony zinc oxide (AZO) etc., the wherein leading position of ITO material occuping market.
Along with transparent conducting coating obtains a wide range of applications, people it is also proposed higher requirement to its performance index.The major defect of ITO class transparent conductive material is: 1, indium is rare earth element, and resource-constrained is expensive; 2, ito thin film mainly adopts the technology such as vacuum sputtering, evaporation to prepare, complex manufacturing, and cost is high, the more difficult preparation of large scale exemplar; 3, ito thin film quality is more crisp, and resistance to bending performance is poor, cannot obtain flexible and transparent conductive layer.
In recent years, people have developed much novel electric conducting material, it is desirable to substitute ITO material.Researcher finds that the coating adopting nano silver wire material to prepare has excellent conductivity, light transmittance and resistance to bending performance (Polman, A et al.Nano Lett.2012,12,3138-3144, K.S.et al.Adv.Funct.Mater.2013,23,1250 – 1255, Xu, F.; Zhu, Y.Adv.Mater.2012,24,5117-5122.), but nano silver wire material also have simultaneously contact resistance higher, with the shortcoming (I.A.et al.Nanoscale Res Lett 2013,8,235.) such as substrate tack is poor, corrosion resistance is not strong.
Stanford Univ USA finds electrogilding film in silver nanowire layer and carries out the contact resistance that hot-pressing processing can reduce between the lines; Found again that adopting tungsten halogen lamp to irradiate can make nano silver wire crosspoint weld together at low temperatures afterwards, further reduce the contact resistance between nano silver wire, the transparent conducting coating light transmittance sheet resistance 80% time obtained only has 10 Ω/ (Hu, L.et al.ACS nano 2010,4,2955-2963.Brongersma, M.L.et al.Nat Mater 2012,11,241-249.).
Although these methods can reduce the contact resistance of silver-colored line effectively, the corrosion resistance improving coating is not acted on.A seminar of California, USA university first applies one deck TiO at nano silver wire coating surface
2colloidal sol, is coated with one deck conducting polymer PEDOT:PSS again, obtains nano silver wire-TiO after oven dry
2-PEDOT:PSS composite coating; This Adhesion of Multi-Coatings of lon, corrosion resistance all improve a lot, but the raw material needed is more, and step is more loaded down with trivial details, is not suitable for large area film forming (Li, G.et al.ACS nano2011,5,9877-9882.).
CN 102087886 A first applies one deck adhesive (as PVA) at substrate surface, then applies nano silver wire, the composite coating obtained after super-dry.Although this method makes the tack of coating increase substantially, reduce the conductivity of coating.
Also the Graphene compound that nano silver wire and chemical vapour deposition technique (CVD) are prepared by many seminar is had in addition, adopted process for preparing graphenes by chemical vapour deposition on the metallic substrate before this, then transfer on silver coating by Graphene from metallic substrates, transfer method has matrix corrosion method etc.Although the composite coating conductivity that described method obtains and tack are all significantly improved, but process for preparing graphenes by chemical vapour deposition, cost is higher, complex process, and the high-quality transfer process of Graphene is also a great problem, (CN 103325442 A, CN 203085198 U, Alam, M.A.et al.Adv.Funct.Mater.2013,23,5150-5158).
A kind of preparation method of transparent conductive film is urgently developed in this area, and it can improve conductivity, the adhesive force of nano silver wire coating, simultaneously simple, the low production cost of its technique.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide that a kind of light transmittance is high, good conductivity, corrosion resistance be strong, be particularly useful for transparent conductive film of various flexible touch screen device and preparation method thereof.The preparation method of transparent conductive film provided by the invention, can large-scale production without the need to vacuum equipment, without the need to high temperature, simple for process, be applicable to the substrate of any area or shape.
The present invention is achieved through the following technical solutions:
An object of the present invention is the preparation method providing a kind of graphene oxide/nano silver wire composite transparent conductive coating, and described method comprises the steps:
(1) substrate is provided;
(2) silver coating nano wire in substrate, obtains nano silver wire conductive layer;
(3) on silver nanoparticle conductive layer, continue coating graphene oxide, obtain graphene oxide layer;
The oxygen-containing functional group of graphene oxide is more, be macroscopically the material of the non-constant of a kind of conductivity, graphene oxide and nano silver wire coating compound, do not reducing the conductivity of nano silver wire coating, unexpectedly on the contrary improve its conductivity, keep higher light transmittance simultaneously.Graphene oxide has set up conductive channel between nano silver wire, improves its conductivity; Graphene oxide and substrate have Physical interaction strongly, overcome nano-silver conductive layer and substrate adhesion is little, oxidative resistance is poor shortcoming, improve the useful life of composite conductive thin film.
The C/O ratio of graphene oxide of the present invention is 0.3 ~ 2.5, such as 0.4,0.5,0.9,1.3,1.6,2.0,2.3,2.4 etc.
Preferably, resistance value>=10 of described graphene oxide
8Ω/, such as 2 × 10
8Ω/, 7 × 10
8Ω/, 10
9Ω/, 5 × 10
9Ω/ etc.
Preferably, the applied thickness of described graphene oxide is 1 ~ 100nm, such as 2nm, 5nm, 25nm, 36nm, 42nm etc., is more preferably 5 ~ 50nm.
The solvent kind of described graphene oxide dispersion is not specifically limited, and can be used in disperseing the solvent of graphene oxide all to can be used as the solvent of graphene oxide dispersion.
Preferably, the concentration of described graphite oxide dispersion is 0.25 ~ 5mg/mL, such as 0.3mg/mL, 0.6mg/mL, 0.9mg/mL, 1.3mg/mL, 2.5mg/mL, 3.6mg/mL, 4.9mg/mL etc.
Preferably, in described graphene oxide dispersion, the size of graphene oxide lamella is selected from 0.5 ~ 50 μm, such as 0.6 μm, 4 μm, 12 μm, 25 μm, 36 μm, 47 μm etc., preferably 5 ~ 50 μm.
The diameter of nano silver wire of the present invention is 10 ~ 100nm, and length is 5 ~ 60 μm.
Typical but non-limiting nano silver wire is of a size of: diameter 12nm, length 10 μm; Diameter 20nm, length 50 μm; Diameter 60nm, length 30 μm; Diameter 70nm, length 60 μm etc.
Preferably, the applied thickness of described nano silver wire is 40 ~ 5000nm, such as 52nm, 80nm, 135nm, 150nm, 540nm, 800nm, 1052nm, 3500nm, 4500nm etc., preferably 200 ~ 1000nm.
Preferably, the method for the coating described in step (2) is: the compound mode adopting any a kind or at least 2 kinds in spin coating, blade coating, dip-coating or spraying, by nano silver wire dispersed liquid coating in substrate;
Preferably, the solvent of described nano silver wire dispersion liquid is selected from the combination of any a kind or at least 2 kinds in deionized water, ethanol, isopropyl alcohol;
Preferably, the concentration of described nano silver wire dispersion liquid is 0.1 ~ 1mg/mL.
Step (2 ') hot pressing nano silver wire conductive layer is carried out after step of the present invention (2);
Preferably, described hot pressing temperature is 80 ~ 120 DEG C; Hot pressing pressure is 10 ~ 50MPa; Hot pressing time is 60 ~ 300s;
Preferably, described hot pressing temperature is 100 DEG C; Hot pressing pressure is 20MPa; Hot pressing time is 120s.
The method of the coating described in step (3) is: the compound mode adopting any a kind or at least 2 kinds in spin coating, blade coating, dip-coating or spraying, is coated in graphite oxide dispersion on silver nanoparticle conductive layer.
The method of coating of the present invention is typical but non-limiting comprises spraying process, knife coating, spin-coating method, dip coating etc., and from the viewpoint of formation efficiency, preferred spraying process etc. can continuous cambial method.
Step (3 ') heat-treatment oxidation graphene layer is carried out after step of the present invention (3);
Preferably, described heat treated temperature is 80 ~ 120 DEG C.
Carry out step (1 ') after step of the present invention (1) and preliminary treatment is carried out to substrate;
Preferably, described preprocess method comprises: surface plasma process, or the process of surface application cured resin;
Preferably, described surface plasma processing time≤300s, preferably 5 ~ 30s;
Preferably, described cured resin is selected from light-cured resin or heat reactive resin;
Preferably, the applied thickness of described cured resin is 10 ~ 10000nm, is preferably 20 ~ 200nm.
Step of the present invention (1) described substrate is transparent substrates or opaque substrate; Preferably clear substrate;
Preferably, step (1) described substrate is flexible substrates or rigid basement; Preferred flexible substrate;
Preferably, step (1) described substrate is planar substrates or the substrate with flexure plane; Preferably there is the substrate of flexure plane.
The material of step of the present invention (1) described substrate is selected from any a kind in polymethyl acrylate, Merlon, PETG, polystyrene, polyamide, polyimides, polysulfones, polyether sulfone, polyformaldehyde, glass, pottery; Any a kind in preferred polymethyl methacrylate, Merlon, PETG, polystyrene.
As optimal technical scheme, the preparation method of graphene oxide of the present invention/nano silver wire composite transparent conductive coating comprises the steps:
(1) substrate is provided;
(1 ') carries out surface plasma process to substrate, or the process of surface application cured resin;
(2) silver coating nano wire in substrate, obtains nano silver wire conductive layer;
(2 ') hot pressing nano silver wire conductive layer;
(3) on silver nanoparticle conductive layer, continue coating graphene oxide, obtain graphene oxide layer;
(3 ') heat-treatment oxidation graphene layer.
Present invention also offers graphene oxide/nano silver wire compound transparent electricity conductive film that a kind of method as previously mentioned prepares, described conductive coating comprises nano silver wire conductive layer, and is coated in the graphene oxide layer on nano silver wire conductive layer.Fig. 1 is the structural representation of graphene oxide/nano silver wire conductive layer composite conductive thin film prepared by the present invention.
Compared with prior art, the present invention has following beneficial effect:
(1) graphene oxide provided by the invention/nano silver wire compound transparent electricity conductive film adopts graphene oxide and nano silver wire compound, not only do not have because the weak inductive of graphene oxide reduces the conductivity of nano silver wire, improve the conductivity of nano silver wire on the contrary, and improve adhesive force, the oxidative resistance of nano silver wire coating and substrate simultaneously, improve useful life;
(2) well, as conductivity can up to 32omh/sq, light transmission is up to 93% for graphene oxide provided by the invention/nano silver wire compound transparent electricity conductive film conductivity and light transmission;
(3) graphene oxide provided by the invention/nano silver wire compound transparent electricity conductive film can be coated in the substrate of flexibility or rigidity, on the basis of not losing conductivity and light transmission, can bend, reels or be cut into any use size;
(4) graphene oxide provided by the invention/nano silver wire compound transparent electricity conductive film is prepared by wet processing, and technique is simple, and applicability is strong, can be applicable to the article applying any shape, be easy to realize industrialized production.
Accompanying drawing explanation
Fig. 1 is the structural representation of graphene oxide/nano silver wire conductive layer composite conductive thin film prepared by the present invention;
Fig. 2 is the scanning electron microscope (SEM) photograph of the laminated film that obtains of embodiment 3 at silicon chip surface;
Fig. 3 is the scanning electron microscope (SEM) photograph of the laminated film that obtains of embodiment 6 at silicon chip surface.
Embodiment
Below be only preferred embodiment of the present invention, scope of the present invention can not be limited with this.Namely the equalization generally done according to the present patent application the scope of the claims changes and modifies, and all still should belong to the scope that patent of the present invention contains.Structure of the present invention and preparation method is illustrated below by embodiment.
Embodiment 1 provides one to be coated in suprabasil graphene oxide/nano silver wire compound transparent electricity conductive film, prepares by the following method:
(1) nano silver wire is prepared:
In 50g ethylene glycol, dissolve 0.30gPVP and 5mgCTAB, be placed in there-necked flask and reflux at 150 ~ 170 DEG C 30min, magnetic stirring apparatus Keep agitation in whole course of reaction; Then slowly add the ethylene glycol solution of the silver nitrate of 10g 2wt%, after continuing reaction 30 ~ 90min, stop heating; Take out the acetone diluted that the solution reacted adds about 3 times of volumes, in the centrifugal 1min of 2000rpm, after the dispersion of precipitation 50mL deionized water, continue the acetone diluted adding 3 times of volumes, centrifugal, repeat the nano silver wire obtaining for 3 times purifying;
(2) nano silver wire conductive layer is prepared:
Use 2-isopropoxide ethanol to be diluted to concentration for 0.25mg/mL nano silver wire prepared in step (1), be sprayed on PETG (PET) substrate surface; Then at 100 DEG C, heating removes desolventizing;
Press down 120s with film laminator with the pressure 100 DEG C of 20MPa, obtain nano silver wire conductive layer;
Four probe method is adopted to measure the surface resistivity of nano silver wire conductive layer afterwards; Measure the resistance to tape-stripping performance of nano silver wire conductive layer;
(3) graphene oxide layer is applied
By the method for spin coating, graphene oxide dispersion be coated in the PET base being coated with nano silver wire conductive layer that step (2) obtains, rotating speed is 2000rpm, obtains the composite construction of graphene oxide/nano silver wire/PET, then at 100 DEG C, be incubated 1h, make it dry;
The formation method of nano silver wire conductive layer provided in the present embodiment and graphene oxide layer just schematically, other any methods that can form described nano silver wire conductive layer and graphene oxide layer all replace described method, such as can use spin coating, the method for blade coating or dip-coating replaces spraying, form nano silver wire conductive layer; Spin coating is replaced by the method for blade coating, dip-coating or spraying.
Embodiment 1 ~ 10 provides coating graphene oxide on the pet substrate/nano silver wire compound transparent electricity conductive film, and except the condition described in table 1, concrete operating process is identical with embodiment 1.
The experiment condition of table 1 embodiment 1 ~ 10
Performance test
Graphene oxide embodiment 1 ~ 10 provided/nano silver wire compound transparent electricity conductive film carries out performance test, tests respectively:
1. surface resistivity: adopt four probe method to measure the surface resistivity of nano silver wire conductive layer;
2. resistance to tape-stripping performance: Scotch adhesive tape (3M) is pasted on sample surfaces, adhesive tape is firmly rubbed to ensure coating and adhesive tape comprehensive engagement with finger tip, then on sample, add the weight of 1kg, after 1min, arrest one end that adhesive tape is unsettled, and with the angle of 60 °, in 1s, tear off adhesive tape reposefully, then measure its electric conductivity by four probe method; After test tape pastes 1 time respectively, the surface resistivity (Ω/) of coating, and after test tape pastes 10 times respectively, the surface resistivity (Ω/) of coating;
3. coating adhesion: the adhesive force measuring coating according to standard ISO 2409:2007, GB/T 9286-1998.Grid cutter adopts BYK SISI206, and adhesive tape adopts Scotch (3M), uses magnifying glass to observe coating surface after test.The size accounting for the gross area using disbonding area is that adhesive force is good as adhesive force criterion: < 5%; 5%-15% is that adhesive force is general; >=15% is poor adhesive force.
4. water resistance: under room temperature, the composite construction of graphene oxide/nano silver wire/PET to be soaked in completely in deionized water and to keep the constancy of volume of water, after reaching soak time, sample is taken out, by washed with de-ionized water, re-use the residual water droplet of active paper removing, measure its electric conductivity by four probe method;
5. resistant to acetone performance: under room temperature, being soaked in completely by the composite construction of graphene oxide/nano silver wire/PET in acetone and keeping the constancy of volume of acetone, after reaching soak time, taken out by sample, drying at room temperature, measures its electric conductivity by four probe method;
6. resistance to isopropyl alcohol performance: under room temperature, the composite construction of graphene oxide/nano silver wire/PET to be soaked in completely in isopropyl alcohol and to keep the constancy of volume of isopropyl alcohol, after reaching soak time, sample is taken out, re-use the residual drop of active paper removing, drying at room temperature, measures its electric conductivity by four probe method;
7. high-temp resisting high-humidity resisting degree performance: sample being placed in relative humidity is 90%, temperature is the climatic chamber (KCL-2000W of 60 DEG C, TOKYO RIKAKIKAI Co., LTD) in, after a period of time, sample is taken out, and after ambient temperatare puts 24h, measures its electric conductivity by four probe method.
8. bend resistance fatigue behaviour: the two ends of sample are fixed on drawing stand and carry out bi-directional compression, compression speed is 1.5mm/min, stops compressing and recovering deformation to 0%, in this, as once bending when compressive deformation reaches 100%; Then above-mentioned bending experiment is repeated, the electric conductivity of sample under employing four probe method mensuration different bending number of times; Test the electric conductivity under bending number of times 50 times, 500 times and 1000 times respectively;
9. light transmittance: is the light transmittance of 200 ~ 1000nm in optical wavelength with ultraviolet/visible/near infrared spectrophotometer (Lambda 950) test sample;
The performance test results of embodiment 1 ~ 5 is as shown in table 2:
The performance test results of table 2 embodiment 1 ~ 5
The performance test results of embodiment 6 ~ 10 is as shown in table 3:
The performance test results of table 3 embodiment 6 ~ 10
As can be seen from embodiment 1-5, nano silver wire coating is thicker, and the conductivity of coating is better, but the light transmittance of coating can obviously reduce.The resistance to tape-stripping of coating, solvent resistance, high-temp resisting high-humidity resisting and bend resistance performance all increase.Contrasted as can be seen from embodiment 1,4,5 and 6,7,8, graphene oxide layer can significantly improve the conductivity of coating, resistance to tape-stripping, solvent resistance, high-temp resisting high-humidity resisting and bend resistance performance.Contrasted as can be seen from embodiment 7,8,9, graphene oxide layer is thicker, more obvious to the lifting of the conductivity of coating, resistance to tape-stripping, solvent resistance, high-temp resisting high-humidity resisting and bend resistance performance, and light transmittance can be caused time too thick slightly to decline.The main cause that conductivity improves is owing to having strong interaction containing the graphene oxide and substrate that enrich oxygen-containing functional group, the nano silver wire be between graphene oxide with substrate can be contacted more closely, thus reduce the contact resistance between nano silver wire.Graphene oxide forms continuous print film on nano silver wire, as protective layer, can slow down the oxidizing process in the presence of a harsh environment of nano silver wire, thus improves solvent resistance and the high-temp resisting high-humidity resisting of coating.Graphene oxide can also prevent loosening and coming off from substrate in bending distortion between nano silver wire, thus improves the bend resistance performance of nano silver wire coating.
Embodiment 11 ~ 13 each provides one and is coated in suprabasil graphene oxide/nano silver wire compound transparent electricity conductive film, is with the difference of embodiment 10, and substrate respectively is PC, PMMA, glass.
Performance test:
Suprabasil graphene oxide/nano silver wire the compound transparent electricity conductive film that is coated in embodiment 11 ~ 13 provided carries out the test of conductivity, resistance to tape-stripping, solvent resistance, high-temp resisting high-humidity resisting and light transmittance properties, method of testing is identical with the method for testing of embodiment 1 ~ 6, and test result is as shown in table 4:
The performance test results of table 4 embodiment 11 ~ 13
As can be seen from Table 4, on the organic of inflexibility and inorganic substrates, graphene oxide can both improve the conductivity of coating, resistance to tape-stripping, solvent resistance and high-temp resisting high-humidity resisting well, and this method is a kind of more common method, can implement in most of substrate.
Embodiment 14 ~ 18 each provides one and is coated in suprabasil graphene oxide/nano silver wire compound transparent electricity conductive film, be with the difference of embodiment 1, before step (2) prepares nano silver wire conductive layer, plasma treatment is carried out to pet sheet face, power is 200W, processing time respectively is 20s, 40s, 60s, 90s, 120s, and adopts the full-automatic contact angle measurement of DSA100 to measure water contact angle after the treatment;
Suprabasil graphene oxide/nano silver wire the compound transparent electricity conductive film that is coated in embodiment 14 ~ 18 provided carries out conductivity, resistance to tape-stripping, solvent resistance, high-temp resisting high-humidity resisting, bend resistance performance and light transmission performance test, method of testing is identical with the method for testing of embodiment 1 ~ 6, and test result is as shown in table 5:
The performance test results of table 5 embodiment 14 ~ 18
As can be seen from Table 5, along with the increase of plasma treatment time, the water contact angle of substrate first diminishes, then become large, the conductivity variation tendency of composite coating is identical with family feeler variation tendency, namely contact angle is less, and the conductivity of composite coating, resistance to tape-stripping, solvent resistance, high-temp resisting high-humidity resisting and bend resistance performance are better.This is because graphene oxide is due to containing a lot of oxygen-containing functional group, show good hydrophily, plasma treated surface hydrophilicity grow, the interaction between graphene oxide and substrate is made to become stronger, thus make the contact between nano silver wire more tight, conductivity is improved.
Embodiment 19 ~ 20 each provides one and is coated in suprabasil graphene oxide/nano silver wire compound transparent electricity conductive film, be with the difference of embodiment 10, after having prepared nano silver wire conductive layer, carry out plasma treatment again, the processing time is 20s, and power is 200W; Number of processes is followed successively by 1 time, 2 times; And adopt the full-automatic contact angle measurement of DSA100 to measure water contact angle after the treatment;
Suprabasil graphene oxide/nano silver wire the compound transparent electricity conductive film that is coated in embodiment 19 ~ 23 provided carries out the performance tests such as conductivity, resistance to tape-stripping, solvent resistance, high-temp resisting high-humidity resisting, bend resistance performance and light transmission, method of testing is identical with the method for testing of embodiment 1 ~ 6, and test result is as shown in table 6:
The performance test results of table 6 embodiment 19 ~ 20
As can be seen from Table 6, surface treatment is being carried out after surface-treated substrate coating nano silver wire, the hydrophily on surface can be improved further, but the conductivity of coating does not then improve further, compared with not carrying out the sample of second time plasma treatment, coated conductive, resistance to tape-stripping, solvent resistance, high-temp resisting high-humidity resisting and bend resistance performance decline all to some extent.This is because in second time plasma treatment procedure, nano silver wire destroys in the bombardment of plasma, and become chain pearl, conductive path destroys, and conductivity is declined.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for graphene oxide/nano silver wire compound transparent electricity conductive film, is characterized in that, described method comprises the steps:
(1) substrate is provided;
(2) silver coating nano wire in substrate, obtains nano silver wire conductive layer;
(3) on silver nanoparticle conductive layer, continue coating graphene oxide, obtain graphene oxide layer.
2. the method for claim 1, is characterized in that, the C/O ratio of described graphene oxide is 0.3 ~ 2.5;
Preferably, resistance value>=10 of described graphene oxide
8Ω/;
Preferably, the applied thickness of described graphene oxide is 1 ~ 100nm, is more preferably 5 ~ 50nm;
Preferably, the concentration of described graphite oxide dispersion is 0.25 ~ 5mg/mL;
Preferably, in described graphene oxide dispersion, the size of graphene oxide lamella is selected from 0.5 ~ 50 μm, preferably 5 ~ 50 μm.
3. method as claimed in claim 1 or 2, it is characterized in that, the diameter of described nano silver wire is 10 ~ 100nm, and length is 5 ~ 60 μm;
Preferably, the applied thickness of described nano silver wire is 40 ~ 5000nm, preferably 200 ~ 1000nm;
Preferably, the method for the coating described in step (2) is: the compound mode adopting any a kind or at least 2 kinds in spin coating, blade coating, dip-coating or spraying, by nano silver wire dispersed liquid coating in substrate;
Preferably, the solvent of described nano silver wire dispersion liquid is selected from the combination of any a kind or at least 2 kinds in deionized water, ethanol, isopropyl alcohol;
Preferably, when selecting spraying method to carry out nano silver wire dispersion, the concentration of nano silver wire dispersion liquid is 0.1 ~ 1mg/mL.
4. the method as described in one of claims 1 to 3, is characterized in that, carries out step (2 ') hot pressing nano silver wire conductive layer after step (2);
Preferably, described hot pressing temperature is 80 ~ 120 DEG C; Hot pressing pressure is 10 ~ 50MPa; Hot pressing time is 60 ~ 300s;
Preferably, described hot pressing temperature is 100 DEG C; Hot pressing pressure is 20MPa; Hot pressing time is 120s.
5. the method as described in one of Claims 1 to 4, it is characterized in that, the method of the coating described in step (3) is: the compound mode adopting any a kind or at least 2 kinds in spin coating, blade coating, dip-coating or spraying, is coated on silver nanoparticle conductive layer by graphite oxide dispersion;
Preferably, step (3 ') heat-treatment oxidation graphene layer is carried out after step (3);
Preferably, described heat treated temperature is 80 ~ 120 DEG C.
6. the method as described in one of Claims 1 to 5, is characterized in that, carries out step (1 ') and carry out preliminary treatment to substrate after step (1);
Preferably, described preprocess method comprises: surface plasma process, or the process of surface application cured resin;
Preferably, described surface plasma processing time≤300s, preferably 5 ~ 30s;
Preferably, described cured resin is selected from light-cured resin or heat reactive resin;
Preferably, the applied thickness of described cured resin is 10 ~ 10000nm, is preferably 20 ~ 200nm.
7. the method as described in one of claim 1 ~ 6, is characterized in that, step (1) described substrate is transparent substrates or opaque substrate; Preferably clear substrate;
Preferably, step (1) described substrate is flexible substrates or rigid basement; Preferred flexible substrate;
Preferably, step (1) described substrate is planar substrates or the substrate with flexure plane; Preferably there is the substrate of flexure plane.
8. the method as described in one of claim 1 ~ 7, it is characterized in that, the material of step (1) described substrate is selected from any a kind in polymethyl acrylate, Merlon, PETG, polystyrene, polyamide, polyimides, polysulfones, polyether sulfone, polyformaldehyde, glass, pottery; Any a kind in preferred polymethyl methacrylate, Merlon, PETG, polystyrene.
9. the method as described in one of claim 1 ~ 8, is characterized in that, described method comprises the steps:
(1) substrate is provided;
(1 ') carries out surface plasma process to substrate, or the process of surface application cured resin;
(2) silver coating nano wire in substrate, obtains nano silver wire conductive layer;
(2 ') hot pressing nano silver wire conductive layer;
(3) on silver nanoparticle conductive layer, continue coating graphene oxide, obtain graphene oxide layer;
(3 ') heat-treatment oxidation graphene layer.
10. the graphene oxide that method prepares as described in one of claim 1 ~ 9/nano silver wire compound transparent electricity conductive film, it is characterized in that, described conductive film comprises nano silver wire conductive layer, and is coated in the graphene oxide layer on nano silver wire conductive layer.
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