CN105761774A - Novel electrode material applicable to intelligent liquid crystal dimming film and preparation method thereof - Google Patents
Novel electrode material applicable to intelligent liquid crystal dimming film and preparation method thereof Download PDFInfo
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- CN105761774A CN105761774A CN201410791140.5A CN201410791140A CN105761774A CN 105761774 A CN105761774 A CN 105761774A CN 201410791140 A CN201410791140 A CN 201410791140A CN 105761774 A CN105761774 A CN 105761774A
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Abstract
The invention relates to a novel electrode material applicable to an intelligent liquid crystal dimming film and a preparation method thereof. A transparent conductive film is at least composed of a substrate and a graphene conductive layer. The transparent conductive film further comprises a functional layer. Graphene sheets are stacked, tiled and connected with one another on a substrate to form the graphene conductive layer. A flexible liquid crystal dimming film device is prepared through the whole wet coating process of the electrodes of a graphene transparent conductive film. The liquid crystal light adjusting layer of the commercialized flexible liquid crystal dimming film is also prepared through the wet coating process. The above two coating processes can be linked up through the roll-to-roll process. Therefore, the preparation of graphene transparent conductive electrodes and the subsequent preparation of the dimming film are ensured to be continuous, low in cost and large-scale in production.
Description
Technical field
The present invention relates to a kind of graphene transparent electrode material prepared with native graphite alkene and preparation method thereof, a kind of electrode material of intelligence electroluminescent light modulation film device being applied to liquid crystal system and preparation method thereof.
Background technology
Intelligent light modulation film is a kind of photoelectric device, and it is the input by the signal of telecommunication thus changes the device of the optical parametrics such as the light transmittance of light modulation film, mist degree.It is often used in the fields such as external wall, house property decoration, vehicle glass, automobile rearview mirror, projection curtain wall, office space, public entertainment facility.Apply the smart window on such as building by the most typically of intelligent light modulation film as a example by, intelligent light modulation film by attaching, the mode such as clamping is combined with building glass, by input electrical signal on light modulation film thus regulation from the incident light intensity of glass forms, thus reach energy-conservation purpose.
Usual intelligent electroluminescent light modulation film device, is to be made up of the light regulating course of two transparency conductive electrode material layers and middle clamping.The electrode material being widely used at present is tin indium oxide (ITO) electrode, and its basic structure is one layer of ITO conductive material of attachment in transparent substrates.But intelligent light modulation film is still difficult to commercially spread at present, reason is to there is also problems as the transparent conductive electrode material of light modulation film core: one, the main component indium of ITO is scarce resource and expensive, the cost of raw material is higher, and construction material is difficult to bear its cost；Two, by methods such as sputtering, evaporations, the processing of ITO conductive layer realizes that not only energy consumption is high but also waste of raw materials serious mostly, therefore its technique manufacturing cost is the highest；Three, ITO is a kind of oxide semiconductor material, and fragility is difficult to greatly realize the functions such as bending, folding, hinders its further application in smart window technology；Four, the reflectance of ITO is higher, and easily causes flavescence because of illumination when preserving.
And emerging ITO substitution material Graphene is as a kind of Two-dimensional Carbon nano material, its thickness only has 0.34 nanometer, and it is almost fully transparent, only absorbs the light of 2.3%；Under room temperature, its electron mobility is more than 15000 cm2/ V s, and resistivity about 10-8Ω m is lower than copper or silver, for the material that resistivity in the world is minimum.Graphene transparency conductive electrode material has possessed the unrivaled advantage of ITO and performance, and carbon is the abundantest in nature so that the cost of raw material of Graphene is the cheapest.In theory, Graphene is the preferred plan substituting ITO.
But, up to the present, Graphene transparency conductive electrode is not the most successfully applied in intelligent light modulation film field.One main cause is that the commonly used CVD of current industrial quarters prepares graphene transparent conductive film, although its cost of raw material is relatively low but its manufacturing cost is the highest, therefore it is difficult to apply on light modulation film.Invention CN103760722A discloses a kind of light modulation film using Graphene as electrode and preparation method thereof, but on the basis of being built upon, due to intelligent light modulation film, the Graphene transparency conductive electrode prepared with CVD, high manufacturing cost makes it be difficult to have commercialization and practical value.
Summary of the invention
For the problem solving Graphene transparency conductive electrode cost degradation, the present invention proposes a kind of method preparing Graphene transparency conductive electrode for raw material low cost with the native graphite alkene existed in nature, the performance of this electrode material is completely suitable for flexible intelligent liquid crystal light modulation film, and its cheap manufacturing cost is also fully consistent with the large-scale application of flexible intelligent liquid crystal light modulation film.
The technical solution used in the present invention is:
A kind of flexible intelligent light modulation film device electrode material, described electrode material is the transparent conductive film being made up of native graphite alkene, this thin film is at least made up of graphene conductive layer and substrate layer, optional also comprises functional layer, and described intelligent dimming membrane module refers to electroluminescent light modulation film device based on liquid crystal material.
The basic structure that described native graphite alkene refers to wherein Graphene be in nature through long-term Geological Evolution the graphene-structured of self-assembling formation, including graphene-structured present in native graphite, coal and/or oil.
Described native graphite alkene preferred natural graphite.Described graphene conductive layer, it is characterised in that described graphene conductive layer is the graphene conductive layer sprawled on substrate by a large amount of native graphite alkene thin slices, stacked, be interconnected to form；Described graphene platelet is interconnected to form the connected mode of conductive layer and includes that a connection, line connect, face connects, three-dimensional connects or the mixing of aforementioned connected mode.Described functional layer is any one or more in protective layer, antireflection layer, anti-dazzle photosphere, barrier layer, tack coat.
Described substrate layer is transparent flexible substrate layer, including Merlon, silica gel, polrvinyl chloride, polyethylene terephthalate, polystyrene, polymethylacrylic acid, glass resin, polypropylene, fluoropolymer, polyimides, polyamide, polyether-ether-ketone resin, polynorbornene, polyester, polyvinyl, acrylonitrile-butadiene-styrene copolymer, silica gel or the copolymer of above-mentioned polymer, mixture and combinations thereof.Described substrate layer is preferably polyethylene terephthalate (PET).Described transparent conductive film is 60-95% at 550 nm visible region light transmittances, and surface resistance is 0.2-30 K Ω/.
A kind of preparation method of flexible intelligent light modulation film device electrode material, with the material rich in native graphite alkene as raw material, chemical stripping method, physics stripping method or a combination thereof mode is used to be stripped out by grapheme material therein, form graphene dispersing solution, then graphene dispersing solution is coated with on flexible substrates.
Before the coating, described flexible substrate will be through pre-treatment；After coating, in addition it is also necessary to through post processing.The described material rich in native graphite alkene include native graphite, coal, coal tar, black petroleum products one or more, one or more in the most natural flaky graphite or expanded graphite.Described physics stripping method utilizes physical action to be eliminated by graphite layers active force in the case of main conjugated structure in not destroying graphite linings and obtains Graphene.Described chemical stripping method utilizes chemical action to insert active substance in graphite layers thus eliminates graphite layers active force and obtain Graphene.The Graphene that described employing chemical stripping method, physics stripping method or a combination thereof mode are stripped out, the form of its Graphene includes the flawless Graphene in surface, the defective Graphene in surface, graphene oxide, chemical modification Graphene, functionalization graphene or the combination of foregoing graphites alkene.
Described coating process refers to can be used for the various wet coating processes of volume to volume coated technique, is coated with including spraying, blade coating, rod, nick coating, slot die coating, lip mould is extrusion coated and comma coating.Described pre-treatment generally includes heat treatment, physical cleaning, Chemical cleaning, UV ozone process, Plasma process, Corona discharge Treatment, pressure treatment or the combination of aforementioned processing.Described post processing refers to the processing method improving graphene film electric conductivity further with light transmission, including doping treatment, reduction treatment, UV process, cured, electron beam treatment, radiation treatment, heat treatment, physical cleaning, Chemical cleaning, UV ozone process, Plasma process, Corona discharge Treatment, pressure treatment or the combination of aforementioned processing.
The application of above-mentioned electrode material, it is for providing a kind of novel transparent graphene conductive film window electrode with native graphite alkene as construction unit, and preparation is based on liquid crystal type intelligent dimming membrane module.
Flexible light modulation film Graphene transparency conductive electrode
One of main purpose that the present invention wants is to provide a kind of flexible intelligent light modulation film electrode material, and this electrode material is the transparent graphene conductive film constructed for construction unit with native graphite alkene.
Flexible intelligent light modulation film electrode material of the present invention generally includes graphene conductive layer, substrate layer composition, can also include functional layer further.With reference to Fig. 1, in the example embodiment of indefiniteness, it comprises graphene conductive layer 2, substrate 1, functional layer 3.
(
1
) graphene conductive layer
In the present invention, graphene conductive layer is formed by containing the graphene platelet peeled off in native graphite alkene structure, the graphene conductive layer that graphene platelet is sprawled on substrate, stacked, is interconnected to form.Graphene platelet is interconnected to form the connected mode of conductive layer and includes that a connection, line connect, face connects, three-dimensional connects or the mixing of aforementioned connected mode.
Described native graphite alkene structure be in nature through long-term Geological Evolution the graphene-structured of self-assembling formation, mainly include but not limited to graphene-structured present in native graphite, coal, oil, by being stripped out by the Graphene in above-mentioned substance, graphene platelet just can be obtained.
Its shape of described graphene platelet is arbitrary, and its number of plies can be monolayer, it is also possible to be multilamellar, but generally its number of plies is less than 10 layers, belongs to the category of graphite more than 10 layers, is no longer belong to the category of Graphene.
Described graphene conductive layer is to be sprawled on substrate by graphene platelet, stack, be interconnected to form, it is to be appreciated that sprawls and refers to that graphene platelet mainly contacts with each other with its plane and substrate.Furthermore, it is to be appreciated that stacking means be perpendicular on substrate direction to comprise at least one graphene platelet, but also will not be infinite multiple, number and the light transmittance of its stacking be inversely proportional to.Generally the number of stacking is 1 ~ 20.
Point between described graphene platelet links, refer to have point of contact between graphene platelet and exist so that turning between graphene platelet, with reference to Fig. 2, in the example embodiment of an indefiniteness, graphene platelet 201 and graphene platelet 203, be connected with each other by contact point 202.
Line between described graphene platelet links, refer to contact to ensure the conducting between graphene platelet with the presence of one dimensional line between graphene platelet, with reference to Fig. 6, in the example embodiment of an indefiniteness, the one dimensional line 212 that graphene platelet 211 and graphene platelet 213 are consisted of numerous contact point is connected with each other.
Face between described graphene platelet links, refer between graphene platelet with the presence of overlapped region to ensure the conducting between graphene platelet, with reference to Fig. 7, in the example embodiment of an indefiniteness, graphene platelet 221 and graphene platelet 223 also exist overlapping region 222 and are connected with each other.
Three-dimensional link between described graphene platelet, refer to that the space that between graphene platelet, contact surface is formed has three dimensions, thus ensure the conducting between graphene platelet, with reference to Fig. 8, in the example embodiment of an indefiniteness, graphene platelet 231 and graphene platelet 232 are connected to each other by being mutually wound around.
(
2
) substrate
In the present invention, substrate generally refers to the supporting structure for transparency electrode of the present invention.It will also be appreciated by the skilled artisan that to reach flexing, bending function, electrode of the present invention uses flexible substrate, and wishes that substrate has transmittance or transparent.The non-limitative example of suitable substrate includes: Merlon, silica gel, polrvinyl chloride, polyethylene terephthalate, polystyrene, polymethylacrylic acid, glass resin, polypropylene, fluoropolymer, polyimides, polyamide, polyether-ether-ketone resin, polynorbornene, polyester, polyvinyl, acrylonitrile-butadiene-styrene copolymer, silica gel or the copolymer of above-mentioned polymer, mixture extremely combine.
In the present invention, light modulation film is applicable to outdoor environment, usually requires that flexible substrate has the performance of the aspects such as certain anti-flammability, intensity, impact resistance, high-low temperature resistant characteristic, toughness, anti-ultraviolet aging characteristic, antibacterial, antioxidation.It will also be appreciated by the skilled artisan that to realize above-mentioned functions modified, interpolation modifying agent that can be suitable in substrate.The non-limitative example of Suitable modifying agents includes: magnesium salt whisker, glass fibre, calcium carbonate, Pulvis Talci, wollastonite, glass microballoon, mica powder, deca-BDE, eight bromo ether, tetrabromobisphenol A, HBCD, nano imvite, Nano-meter CaCO33, Nano-meter SiO_22, nano-TiO2Deng.
(
3
) functional layer
In the present invention; functional layer is used to regulate the physical chemistry function of transparency electrode or make certain physics chemical action between substrate and conductive layer; described functional layer is not essential, can be any one or more in protective layer, antireflection layer, anti-reflection layer, anti-dazzle photosphere, barrier layer, tack coat.
In the example embodiment of indefiniteness, Fig. 6 illustrates a layer flexible transparency conductive electrode, contains graphene conductive layer 21, substrate 11.Further, multiple structure also include functional layer 31 above conductive layer, functional layer 32 between conductive layer and substrate, functional layer 33 be positioned at the lower section of substrate.It is understood that these functional layers optically should have transparency.Functional layer 31,32,33 has various function, such as, reduce mist degree, reduce reflection, bonding conductive layer and substrate, shield, play barrier layer effect.In some cases functional layer can have multi-functional, such as anti-reflecting layer can simultaneously serve as intercepting barrier layer that extraneous steam enters can also be as the cover plate of protectiveness.
The flexible light modulation film preparation method of Graphene transparency conductive electrode
It is a further object to provide the preparation method of flexible light modulation film Graphene transparency conductive electrode.These methods generally include: (1) provides graphene platelet；(2) graphene platelet coating forms graphene conductive layer.In some embodiments, it is also possible to include that (3) provide functional layer.May also include (4) optimization further to process.
(
1
) graphene platelet is provided
Graphene platelet, is to be stripped out by containing in native graphite alkene structural material, and these natural structures mainly include but not limited in native graphite, coal, oil.Stripping means can include physical method or chemical method, or the mixing of preceding method.
Described physical method is to utilize physical action to be eliminated by graphite layers active force in the case of main conjugated structure in not destroying graphite linings to obtain Graphene.Graphene is found the earliest, is directly to peel Graphene on highly oriented graphite by the viscous glutinous effect of adhesive tape physics.Conventional physical separation methods includes but not limited to: ultrasonic preparation, the stripping of high-speed stirred shearing force, hot lift-off technology, electrochemical stripping, thermal quenching stripping and supercritical liq in the ultrasonic method of solvent supersonic method, surfactant auxiliary, ionic liquid are peeled off.In some embodiments, it is that the graphene platelet in graphite is stripped out by the shearing force produced by high-speed stirred, sees " Scalable production of
large quantities of defect-free few-layer graphene by shear exfoliation in
liquids”(Nature Materials 13,624–630(2014)).Be understandable that physics stripping method, to the precision controllability of graphene platelet more weak such as to the number of plies, size, form control poor, but its technical process is simply suitable for extensive preparation.
More common stripping means is then chemical method, and chemical stripping method utilizes chemical action to insert active substance in graphite layers thus eliminates graphite layers active force and obtain Graphene.Typically include, but not limited to: the stripping of Hummers method, Modified Hummers method, pyrolysis expansion, intercalation stripping method, Coulomb repulsion stripping method, supercritical stripping method, aoxidize ultrasonic stripping method etc..These methods mostly make interlaminar action power die down or eliminate and obtain Graphene by inserting various chemical functional groups in graphite layers.Generally chemical peeling can put more precise control power to good use.“Factors Controlling the
Size of Graphene Oxide Sheets Produced via the Graphite Oxide Route, 5,4,073 4083,2011, ACSNano " middle confirmation, the graphite horizontal peeling rate in oxidizing process and the crack velocity being perpendicular to surface are the keys controlling graphene platelet size.
In embodiments of the present invention, illustrating selection natural flake graphite and utilize hummers stripping means that graphite layers is inserted carboxyl, hydroxyl as raw material, so that the active force of graphite layers eliminates, graphene-structured just is stripped out.Further, the graphite raw material in embodiment is large scale graphite granule, thus controls to obtain more big size graphene thin slice.Owing to chemical peeling is usually formed the oxidised form of Graphene, so the post-processing step generally carried out after chemical peeling includes reduction treatment.
In some embodiments, the graphene platelet obtained by various stripping means is also may pass through further chemical modification, its functional group is increased or decreased.
(
2
) graphene platelet coating formation graphene conductive layer
Graphene conductive layer is that graphene platelet dispersion liquid uses various wet coating processes to be coated with the graphene conductive layer formed on various substrates by volume to volume coated technique.By volume to volume technique to realize the large-scale continuous preparation of Graphene transparency conductive electrode, it is often more important that, in the application of flexible light modulation film, volume to volume technique can realize the serialization of whole process and prepare.
Usually, flexible light modulation film structure is clamping light regulating course in the middle of two flexible and transparent conductive electrodes, and this light regulating course is also applied for volume to volume technique and is applied directly on compliant conductive electrode.Tradition transparent conducting film and CVD are prepared graphene transparent conductive film and are difficult by volume to volume technique and prepare, and cannot realize effective linking of continuous prodution between technology for preparing electrode and follow-up light regulating course.
The selection of coating method is the key factor affecting graphene conductive layer performance, generally be suitable for coating method that volume to volume technique produces including but not limited to: spray, scratch, rod painting, nick coating, slot die coating, extrusion coated, the comma coating of lip mould etc..In an embodiment of the present invention, have employed slot die application pattern to be coated.
In various wet-coating process, graphene platelet is to be used so that dispersion exists.Graphene platelet to be applied can be dissolved in various solvent.The example of these solvents includes, but are not limited to: 1,2-dichloro-benzenes, dimethylformamide, chlorobenzene and toluene, N-Methyl pyrrolidone, dimethyl ether, some lipids and ethers, water, ethanol, methanol, different and alcohol and combinations thereof.In some embodiments, graphene platelet has the form of oxidation state, and its solvent mainly can be, but not limited to select water, ethanol, methanol, isopropanol and combinations thereof.In some embodiments it may be desirable to add surfactant to improve Graphene dispersibility in a solvent, these surfactants can be anion surfactant, cationic surfactant, nonionic surfactant.In more specifically embodiment, usually require that the rheological parameter to graphene dispersing solution is adjusted, can be typically added to viscosity modifier, dispersant, surfactant, anti-settling agent, levelling agent regulate.Concrete discussion, may refer to " Dispersion of graphene in about additive to the performance impact of graphene dispersing solution
aqueous solutions with different types of surfactants and the production of
Graphene films by spray or drop coating, 43,140-146,2012, Journal of the Taiwan Institute of
Chemical Engineers”。
Typical dispersant includes but not limited to: enlightening height auxiliary agent series, Bick auxiliary agent series, maleic anhydride, poly, polyacrylic acid, alkyd resin, the one in these auxiliary chemicals of nanmu or combination.Typical surface modifier includes but not limited to: nonionic fluorocarbon surfactant, Zonyl FSN, Zonyl FSO,
Zonyl® FSH, Triton (×100, ×114, ×45), Dynol (604, 607),
N-Dodecyl b-D-maltoside, enlightening height auxiliary agent, one or more in Bi Ke auxiliary agent etc..Typical viscosities regulator includes but not limited to: carboxymethyl cellulose, dihydroxy ethyl cellulose, hydroxypropyl methyl cellulose, methylcellulose, polyvinyl alcohol, three propyleneglycoles ethers, xanthan gum.Typical anti-settling agent includes but not limited to: Bick auxiliary agent series, enlightening height auxiliary agent series, nanmu this chemical industry anti-settling agent, dibutyl phthalate (DBP), the one in o-phthalic acid dibutyl ester (DOP) or combination.Typical levelling agent includes but not limited to: methyl-silicone oil, polyether modified silicon oil, enlightening height auxiliary agent series or combination.
Generally, substrate needs early stage to process so that more preferable coated graphite alkene conductive layer, such as, make graphene platelet uniform deposition on substrate, or fixing graphene platelet is beneficial to its subsequent treatment.Substrate early stage processes and typically includes, but not limited to: heat treatment, physical cleaning, the cleaning of chemistry, Plasma process, UV ozone process, Corona discharge Treatment or the combination of aforementioned processing.
(
3
) functional layer is provided
Functional layer is provided, can carry out in many ways.In some embodiments; thering is provided protective layer, antireflection layer, antireflection layer, barrier layer, anti-dazzle photosphere, tack coat can be directly fit on volume to volume Coating Production Line protecting film, anti-reflection film antireflective film, Obstruct membrane, anti-dazzling film, and certain all above-mentioned film layers can also be online lower laminating.In other embodiments, it is provided that functional layer can be on line by volume to volume coated technique coating formed.Such as: on volume to volume production line, on substrate, it is directly coated with tack coat by various coated techniques, repastes deposited graphene conductive layer, to strengthen the cementation between graphene conductive layer and substrate.
(
4
) optimization process
Optimization processes the various processing methods referring to improve graphene film electric conductivity further with light transmission, its object processed includes substrate, graphene conductive layer, functional layer or whole graphene transparent conductive film, and processing mode includes but not limited to heat treatment, chemical treatment, radiation treatment or a combination thereof.In some embodiments, processing procedure can be carried out in reducing atmosphere, non-oxidizing atmosphere, vacuum or inert atmosphere.
Generally, substrate is after coated graphite alkene dispersion liquid, and dispersion liquid removes solvent by evaporation, and this last handling process can be through but not limited to: heat, toast, the mode such as microwave, irradiation, purging carrys out acceleration.
In some embodiments, after obtaining graphene conductive layer, have enough conductive capabilities in order to ensure conductive layer.This graphene conductive layer can be through but not limited to: high-temperature heat treatment, electronation process, chemical doping process, pressure treatment, microwave treatment, radiation treatment or a combination thereof process the resistance reducing graphene conductive layer.
In more specifically embodiment, not being resistant to the heat treatment reduction of higher temperature owing to current flexible transparent substrate is mostly polymerizable material, the graphene conductive layer post processing more optimized is cryochemistry reduction treatment, chemical doping process and pressure treatment.Generally cryochemistry processes and may include but be not limited to: low-temperature gaseous phase reduction and low temperature liquid phase are reduced.The main purpose of cryochemistry reduction treatment is to recover the conjugated structure of Graphene, recovers its carrier mobility speed to greatest extent.Conventional low-temperature gaseous phase reduction mode includes but not limited to: hydrazine steam reduction, hydrogen iodide steam, catalytic hydrogenation low-temperature reduction process.Conventional low temperature liquid phase reduction includes but not limited to: hydrazine class compound is (such as: hydrazine, hydrazine hydrate, dimethylhydrazine, phenylhydrazine, to sulfonyloxy methyl hydrazine etc.), metal hydride is (such as: sodium borohydride, lithium aluminium hydride), active metal and oxide thereof are (such as: the aluminum powder under the conditions of acid solution, zinc powder, ferrum oxide, stannum oxide etc.), reducing metal ion is (such as iron ion, magnesium ion, tin ion etc.), reproducibility acid and phenols (ascorbic acid, pyro acid, hydroquinone, tea polyphenols), sodium citrate, alkaline matter is (such as sodium hydroxide, potassium hydroxide, ammonia etc.), reducing sugar is (such as glucose, fructose, sucrose etc.), hydroiodic acid etc..In an embodiment of the present invention, select as a example by hydroiodic acid solution, implement reducing process step.
It is the another kind of mode strengthening graphene conductive layer conductive capability that chemical doping processes, and it is different from electronation and processes, and its Main Function is available to graphene conductive layer more multiple carrier.Common chemical doping processes and includes but not limited to: HNO3、SOCl2、SOBr2、AuCl3And mixed processing.In an embodiment of the present invention, select with AuCl3Doping.
In other embodiments, post processing needs also exist for acting on a functional, such as: after polymer precursor, monomer are coated in substrate, needing further cured to form tack coat, these cured generally can be through but not limited to: ultraviolet light irradiation, radiation of visible light, heating, electron beam irradiation or a combination thereof mode are carried out.
Volume to volume coating processing procedure
It is a further object to provide a kind of volume to volume coating and prepare the processing procedure of Graphene transparency conductive electrode.
Volume to volume coating processing procedure application has high-throughout advantage.It is very suitable for the preparation of the flexible and transparent conductive electrode of the present invention.Volume to volume apparatus for production line is simple, and can automatic operating, the manufacturing cost of transparency conductive electrode can be reduced greatly.Volume to volume coated technique can be that a production line integrated produces, it is also possible to the production line being divided into difference in functionality carries out distribution production.
One nonrestrictive example volume to volume transparency conductive electrode production line 500 is as it is shown in fig. 7, can be applied by continuous print by transmitting path flexible substrate or process.Wind-up roll shaft 511 draws substrate 501, moves along 53 directions from unreeling roll shaft 512.This substrate to experience a series of coating process and processing procedure subsequently on 53 directions.It is understandable that rolling speed, deposition velocity, the concentration of coating and physical parameter and remaining post processing all can affect uniformity and the thickness of the graphene conductive layer of formation.
In coating process subsequently, usual substrate 501 carries out surface process by pre-treatment work station 513 thus strengthens the effectiveness of follow-up Graphene coating.It addition, surface processes the Graphene that can strengthen uniformity that Graphene deposits at substrate surface and the deposition affinity to substrate surface.The mode that generally these surfaces process includes but not limited to: the process of heat treatment, physical cleaning, Chemical cleaning, UV ozone, Plasma process, Corona discharge Treatment, pressure treatment, radiation treatment or the combination of aforementioned processing.Such as: Plasma surface processes the molecular structure that can regulate substrate surface.Utilize gas Plasma, such as Ar, O2、N2 Plasma surface processes and can at room temperature make substrate surface produce the group of high reaction activity.Process due to usual Plasma is only a limited number of layer of surface atom, so the chemical property of bulk substrate is not changed.In many embodiments, Plasma process can strengthen surface infiltration and affinity.In a processing mode exemplary for Plasma, March PX250 can be selected as work station, setup parameter is 150 W, 20 ~ 40 seconds, O2Air-flow: 50 ~ 100 sccm, pressure: 300 ~ 400 mTorr.In other embodiments, pre-treatment work station 513, it is also possible to be coating functional layer on substrate, thus strengthen the affinity of Graphene and substrate.Such as, applying attachment function layer, such functional layer can be fixed Graphene and Graphene can be attached on substrate securely.Certainly pre-treatment work station can also be that surface processes and the combination of functional layer coating.In an exemplary embodiment, such as Fig. 7, pre-treatment work station is coated with one layer of attachment function layer 502 on substrate.
Will enter graphene dispersing solution application job station 514 with back substrate, during coated graphite alkene, graphene dispersing solution 400 forms the wet liquid layer of Graphene 503 by being applied on the surface of tack coat 502.A kind of indefiniteness example graphite alkene application job station 514 constructs, and as shown in Figure 8, raw material memorizer 5111 storage has graphene dispersing solution 400.By coating device 5112, graphene dispersing solution continuous flow 401 is coated on substrate 501 upper surface, thus forms the wet liquid layer of Graphene 503.Generally coating device 5112 includes but not limited to: spray, scratch, rod is coated with, nick coating, slot die coating, lip mould are extrusion coated, comma applying device.It is understood that the functional layer that be there is a need to coating that produces in volume to volume or need to apply the flow process of process, the processing procedure that above-mentioned coated graphite alkene dispersion liquid all can be used to be similar to is coated.
Afterwards, the wet liquid layer of the Graphene of formation 503 layers forms the conductive layer 504 of Graphene by being dried in dry work station 515.Graphene conductive layer 504 will be post-treated work station 516 further and carry out post processing.The usual mode of post processing may include but be not limited to: UV ozone process, Plasma process, Corona discharge Treatment, radiation treatment or the combination of aforementioned processing.Such as 504 surfaces carry out Ar, N2Post processing can strengthen electric conductivity and the light transmittance of graphene conductive layer.In a processing scheme exemplary for Plasma, March PXP250 system can be selected as work station, setup parameter is 150 W, 50 ~ 90 seconds, Ar or N2Air-flow: 5 ~ 20sccm, pressure: 250 ~ 350 mTorr.
As a part for post processing, pressure treatment can strengthen the switching performance between graphene platelet thus strengthen the electric conductivity of graphene conductive layer, and additionally the smooth performance of graphene conductive layer also is able to strengthen.Pressure is applied on 504 layers by roll shaft 517 and 518.The applying of certain this pressure can also repeatedly be carried out, it is also possible to is applied by single roll shaft.The most single roll shaft applying pressure needs that graphene conductive is placed on a hard surface thus is carried out.Generally pressure selects to need an appropriate scope, thus ensures, while strengthening electric conductivity, to be unlikely to graphene platelet damage layer again.
Afterwards, graphene conductive layer 504 enters reduction treatment work station (group) 519 and carries out also principle.Owing to the graphene platelet in graphene conductive layer is the most all to be formed by chemical oxidation stripping means, this is accomplished by carrying out reduction post processing.Reduction post processing can be through but not limited to: heat treatment reduction, low-temperature gaseous phase reduction, low temperature liquid phase reduction or a combination thereof process the resistance reducing graphene conductive layer.Owing to the tolerable temperature of flexible substrate is the most relatively low, the most common mode is low-temperature gaseous phase reduction, low temperature liquid phase reduction.For further, the technological requirement of low temperature liquid phase reduction and equipment requirements are simpler than low-temperature gaseous phase reduction again.Such as: be soaked into 504 in 55%HI acid solution, at 80 ~ 100 DEG C, soak 30s ~ 300s and carry out reduction treatment.It is of course possible to be understood by by person skilled in art, this reduction mode both can be carry out on line can also be online under carry out.After above-mentioned reduction treatment, the conductivity of graphene conductive layer will raise.Showing the most in an embodiment of the present invention, graphene conductive layer is before without reduction treatment, and its surface resistance is about 582K Ω/, and after HI reduction treatment, its surface resistance becomes 1.257K Ω/.If selection liquid-phase reduction processes certainly, it is also possible to wash graphene conductive layer 504 surface and the unnecessary reducing agent of 501 substrate surfaces and the moisture content of residual through further rinsing with dried.Owing to having carried out immersion treatment, liquid phase processes and the Adhering capacity of Graphene and substrate may be made to die down, therefore graphene conductive layer 504 can also carry out pressure treatment further, and this pressure treatment is similar to the pressure treatment mode of roll shaft 517 and 518.It is understood that in the flow process of all immersion treatment functional layers, graphene conductive layer or substrate and the there is a need to immersion treatment of the present invention, all can be in the way of using similar liquid-phase reduction process or the part of mode is implemented.
Afterwards, substrate is pulled into doping treatment work station (group) 520 by wind-up roll shaft 511, and the reagent of usual doping treatment includes but not limited to: HNO3、SOCl2、SOBr2、AuCl3And combinations thereof process.Generally these doping treatment can be by immersion treatment in corresponding solution, it is also possible to be at one layer of solution containing adulterant of 504 coating.The flow process that corresponding immersion treatment work is referred to liquid-phase reduction process is implemented, and coating doping treatment is referred to the coating flow process of graphene dispersing solution and implements.Certainly pressure treatment can also be carried out after doping treatment further.
Afterwards, wind-up roll shaft 511 is by entered function layer processing workstation (group) 521, and these functional layers include: protective layer, antireflection layer, antireflection layer, barrier layer, anti-dazzle photosphere, tack coat.These functional layers both can be coated in the surface of graphene conductive layer 504, it is also possible to is coated in the surface of substrate 501.Implemented can also be to be implemented by application pattern it addition, these functional layers both can be laminating type.Such as: can be direct laminating has shaped on volume to volume Coating Production Line protecting film, anti-reflection film, antireflective film, Obstruct membrane, anti-dazzling film, certain all above-mentioned film layers can also be online lower laminating.In other embodiments, it is provided that functional layer can be on line by volume to volume coated technique coating formed, such as: the coating of tack coat.
Volume to volume preparation flow to this Graphene transparency conductive electrode is basically completed.Graphene conductive layer 504 and substrate 501 are by wind-up roll shaft 511 rolling.
In the processing procedure of this volume to volume, multistep coating and process effectively can be implemented along direction of transfer.Whole volume to volume application system 500 can be customized equally, increases other coating or processing workstation (group) the most on demand.Such as: after polymer precursor, monomer, performed polymer are coated in substrate, needing further cured to form tack coat, these cured typically require increase solidification work station and solidify.
Further, for this Graphene transparency conductive electrode in the application of liquid crystal light modulation film.This volume to volume production line can also continue to increase extraction electrode printing work station, the application job station (group) of liquid crystal polymer, work station (group) of fitting electrode, subsequent treatment and solidification work station.Thus, the processing procedure of the Flexible graphene transparency conductive electrode of this volume to volume can realize continuous prodution and the seamless connection of follow-up liquid crystal light modulation film, not only reduces the cost of transparency conductive electrode and can reduce the production cost of subsequent applications product liquid crystal light modulation film.
Present invention have the advantage that
Those of ordinary skill in the art are it will also be appreciated that the graphene transparent electrode of the present invention provides many advantages.These advantages mainly can include, but are not limited to: (1) low cost；(2) continuous large-area manufacture can be obtained；(3) transparency electrode preparation and the preparation of follow-up light modulation film can realize seamless connection continuous prodution (4) flexibility on equipment and technique.
(
1
) low cost
It is low cost that the present invention prepares the method for transparency electrode.First aspect, the material for novel transparent electrode is the Stable Carbon element of earth high yield, and its native graphite alkene structure reserves on earth formed are huge, therefore the electrode that the present invention provides has the relatively low cost of raw material.Second aspect, the technique prepared for novel transparent electrode is that native graphite alkene is peeled off and separating technology and volume to volume coated technique, and its cost is significantly less than graphene transparent conductive film prepared by the CVD of high energy consumption, therefore the present invention has lower manufacturing cost.
(
2
) continuous large-area manufacture can be realized
The method of the present invention the most easily amplifies scale, and is provided that greater area of transparency electrode.Volume to volume technique belongs to continuously manufacturing, and its kind being not limiting as substrate and size.For the external wall market that light modulation film application market is huge, it usually requires that light modulation film has large area and low cost, requires that transparency conductive electrode has large area and low cost the most exactly.
(
3
) prepared by transparency electrode and the preparation of follow-up light modulation film can realize seamless connection and continuous prodution on equipment and technique
The Graphene transparency conductive electrode of the present invention is prepared based on wet coating technique, and liquid crystal light regulating course is also to use wet coating technique to carry out in current business-like liquid crystal light modulation film, two kinds of coating processes all can use volume to volume technique to be connected, thus realizes the preparation of Graphene transparency conductive electrode and follow-up light modulation film continuous prodution.And prepared by tradition transparent conductive electrode, it is impossible to use the mode of coating to carry out, it is difficult to prepare liquid crystal light regulating course with follow-up coated technique and is effectively connected, it is difficult to realization is extensive, prepared by low cost.
(
4
) flexible
The transparent graphene conductive film electrode of the present invention also demonstrates superpower flexibility.The surface resistance of the membrane electrode that the coating of two-dimensional graphene thin slice is formed on flexible substrates can't be affected by the rich song of thin film and occur substantially to change.This flexibility is extremely important for the application that many disclosed below is possible.
Application
Those of ordinary skill in the art are it is also contemplated that the transparency electrode of the present invention has many application, such as: touch screen, solaode, smart window, OLED display, liquid crystal display, flexible electronic devices etc..But, based on advantages of the present invention, the Graphene transparency conductive electrode of the present invention is more suitable for applying to be prepared on intelligent dimming membrane module in omnidistance volume to volume wet coating.In some more specifically embodiment, it is provided that a kind of novel transparent graphene conductive film window electrode with native graphite alkene as construction unit, this transparency electrode is applicable to prepare intelligent dimming membrane module based on liquid crystal system.
By content described above, it will be recognized by those of ordinary skills, the method and system of the present invention can have other embodiments many.Below with reference to the present invention more specifically some embodiments and for these embodiments provide support experimental result.But, applicant is it is to be noted, that herein below is intended merely to be illustrated more clearly that present disclosure, rather than limits the scope of the claims in the present invention by any way.
Accompanying drawing explanation
The three-decker of Fig. 1 example graphite alkene transparent conductive film electrode
Point connected mode between Fig. 2 example graphite alkene thin slice
Line connected mode between Fig. 3 example graphite alkene thin slice
Face connected mode between Fig. 4 example graphite alkene thin slice
Three-dimensional connected mode between Fig. 5 example graphite alkene thin slice
The five-layer structure of Fig. 6 example graphite alkene transparent conductive film electrode
Fig. 7 example one volume to volume coating processing procedure
Fig. 8 example one application job station.
Detailed description of the invention.
Below in conjunction with embodiment, the present invention is further described.In the examples below, visible light transmissivity and infrared light transmittance are measured with ultraviolet/visible/near infrared spectrophotometer (PerkinElmer Lambda950);Square resistance is measured with double electrical measurement four-point probe (Guangzhou four probe science and technology RTS-9);Film thickness scanning probe microscopy tests (DigitalInstrumentsDimension
3100)。
Embodiment
1
:
Prepared by the chemical stripping of the large scale graphene oxide thin slice with native graphite alkene as construction unit, generally prepare this process of Graphene with chemical stripping method and be divided into low, medium and high temperature process.
(1) material choice:
Large scale requires to select≤100 mesh natural flake graphite powder.Preferred mesh number is≤50 mesh.
(2) chilling process:
By the natural graphite powder of 1 part of quality, the concentrated sulphuric acid of 50 ~ 300 parts of quality, the potassium nitrate of 0.5 ~ 3 part of quality, the potassium permanganate of 3 ~ 15 parts of quality, mix homogeneously is temperature≤10 DEG C in ice bath, react 0.5 ~ 5h.
Preferably, the natural graphite powder of 1 part of quality, the concentrated sulphuric acid of 100 ~ 200 parts of quality, the potassium nitrate of 1 ~ 2 part of quality, the potassium permanganate of 5 ~ 10 parts of quality, temperature≤5 DEG C in ice bath, react 0.5 ~ 3h.
More specifically it is chosen as: the natural graphite powder of 1 part of quality, the concentrated sulphuric acid of 150 parts of quality, the potassium nitrate of 1 part of quality, the potassium permanganate of 6 parts of quality, temperature≤5 DEG C in ice bath, reacts 1h.
(3) middle temperature process:
The reactant liquor of chilling process is heated up, at 20 ~ 50 DEG C, reacts 3 ~ 24h.
Preferably, 30 ~ 40 DEG C, 4 ~ 12h is reacted.
More specifically it is chosen as: 35 DEG C, reacts 6h.
(4) pyroprocess:
In the reactant liquor of middle temperature process, add water, the concentrated sulphuric acid in reactant liquor can in dilution very exothermic, thus maintain pyroreaction, the addition speed of water is the key controlling pyroreaction.
Normally add the water of 30 ~ 60 parts of quality, the addition speed controlling of water in 30 ~ 60min in uniformly add, thus control temperature at 60 ~ 98 DEG C.More extending high-temperature time, can pass through external heat source heat supply, total high temperature response time is 30 ~ 120min.
Preferably, add 40 ~ 50 parts of quality water, the addition speed controlling of water in 30 ~ 45min in uniformly add, temperature is maintained at 80 ~ 98 DEG C, and total high temperature response time is 30 ~ 60min.
More specifically be chosen as: add 45 parts of quality water, the addition speed controlling of water in 30min in uniformly add, temperature is maintained at 90 DEG C, and total high temperature response time is 45min.
(5) cleaning process
Generally cleaning process, including graphene platelet and the separation of reaction liquid.May also include further, the thin classification of Graphene own.By the final Graphene reactant liquor obtained in pyroprocess, by eccentric cleaning until pH value is 4 ~ 7.And be centrifuged 5min by low speed 5000rpm further and isolate big size graphene precipitate, and small size graphene solution.Big size graphene thin slice is dissolved in the water of 500 parts of quality, form the dispersion liquid of Graphene.
Embodiment
2
The high-speed stirred shearing force of the graphene platelet with native graphite alkene as construction unit peels off preparation
The graphite (50 mesh) of a quality and the anhydrous ferric trichloride of six parts of quality are mixed, after put in reactor, then by reactor evacuation, the most again the temperature of reactor is raised to 380 DEG C, and keeps 24 hours；Then the graphite of intercalation is taken out, clean with dilute hydrochloric acid, be baked to after cleaning, intercalated graphite is added water and the ethanol of 50 mass of 50 mass, stir 1 hour under 6000rpm rotating speed.After being filtered cleaning, it is dissolved in N-Methyl pyrrolidone, the Graphene of acquisition is prepared as the solution of 5ml/mg.
Embodiment
3
:
Transparent graphene conductive film is prepared with graphene platelet prepared by chemical stripping method
(1) substrate early stage processes
The 10cm*10cm PET of 5 μ m-thick is used as transparent substrates.PET is put in 150 ° of C baking ovens, aging half an hour；The most again by PET, put into O2 Plasma work station March PX250 process, setup parameter is 150 W, 30 seconds, O2Air-flow: 80 sccm, pressure: 350 mTorr.
(2) coating of attachment function layer
Polymethyl methacrylate (PMMA) is dispersed in dimethyl ether and is configured to the solution that mass concentration is 5%, above-mentioned solution is coated on substrate, remove solvent by drying, obtain the thin film of polymethacrylates.
(3) coating of graphene platelet.
The graphene oxide dispersion that embodiment 1 prepares is coated on PET substrate.Wherein average area >=500 μm 2 of graphene oxide thin slice in dispersion liquid, the mass fraction of graphene oxide may be selected to be, 0.5mg/mL.The coating method used can be any method of the aforementioned proposition of this patent, including: spray, scratch, rod painting, nick coating, slot die coating, extrusion coated, the comma coating of lip mould etc..In the present embodiment, have employed slot die coating.The common range of choice of speed of coating is 0.1 ~ 50m/min.Will be further appreciated that in the case of same coating dispersion liquid, different coating speeds will form different graphene layer thickness, and then affects light transmittance and the conductivity of graphene conductive layer.Further the graphene dispersing solution coating obtained being carried out drying and processing, drying condition is 80 DEG C and keeps 3h, thus will obtain graphene oxide layer.The thickness of graphene oxide layer can be obtained by the measurement of atomic force microscope.Its light transmittance at 550nm can be measured by ultraviolet-uisible spectrophotometer.2
| Coating speed (m/min) | 1.5 | 3 | 5 | 10 | 25 |
| Thickness (nm) | 22.5 | 10.7 | 6.5 | 3.01 | 1.2 |
| GO/PMMA/PET light transmittance (%) | 66.2 | 71.7 | 78.4 | 83.2 | 88.5 |
(4) optimization of graphene conductive layer processes.
It is to strengthen graphene conductive layer electric conductivity that the optimization of graphene conductive layer processes, and reduces the important way of surface resistance.In this embodiment, by as a example by the method for HI acid electronation, the oxygenated functional group on graphene oxide thin slice is dispelled, to recover its conjugated structure, reduce the conductive layer scattering to electronics, strengthen carrier mobility.Further, by graphene conductive layer is carried out AuCl3Doping treatment, strengthens the carrier concentration in graphene conductive layer.By carrier concentration and the common lifting of carrier mobility, strengthen the conductivity of whole transparent conductive film.Further, after chemical doping and electronation, graphene conductive layer can also carry out contacting more closely between pressure treatment, beneficially graphene platelet, reduces contact berrier.It practice, pressure treatment may be located at graphene oxide thin slice coated after carry out, it is also possible to after it is chemically treated.Suitably Stress control is conducive to the contact between thin slice, and can prevent the fracture of the excessive graphene platelet caused of pressure.
Embodiment is, it is coated with the thick graphene oxide conductive layer of 3.01nm by embodiment 2 obtains, immerses in the hydroiodic acid solution that mass fraction is 50%, keep 45 seconds at 100 DEG C, dispel the hydroiodic acid of residual the most again with alcohol washes surface, obtain the graphene conductive layer of reduction.The nitromethane solution of the AuCl3 of coating 13mM further, forms doping after drying on graphene conductive layer surface.Further, with the speed of 10m/min, stainless roller being pressed through the transparent graphene conductive film after doping treatment, pressure is adjusted to 200psi, repeats twice.3
| GO/PMMA/PET | HI reduction treatment | AuCl3Doping treatment | Pressure treatment for the first time | Pressure treatment for the second time | |
| Light transmittance (%) | 83.2 | 82.8 | 80.7 | 80.4 | 80.2 |
| Surface resistance (K Ω/) | 582 | 1.257 | 0.743 | 0.531 | 0.428 |
Embodiment
4
The graphene platelet that example is prepared with physics stripping method prepares transparent graphene conductive film
(1) substrate early stage processes
10cm*10cm PET is put in 150 DEG C of baking ovens, aging half an hour；The most again by PET, put into O2 Plasma work station March PX250 process, setup parameter is 150 W, 30 seconds, O2Air-flow: 80 sccm, pressure: 350 mTorr.
(2) coating of graphene platelet
Graphene sol in embodiment 2 being added N-Methyl pyrrolidone solvent and obtains diluent, the mass concentration of Graphene is 0.5mg/ml.By uniform for mixed liquor mechanical mixture 1h, obtain homodisperse stable dispersion liquid.Take 1ml dispersant liquid drop one end in PET substrate, then use bar to be pulled through dispersion liquid with the speed of 200mm/s, wherein, a diameter of 2mm of bar center line, one layer of uniform wet film is formed on PET surface.Wet film is 50 DEG C of drying.
(3) post processing
With the speed of 10m/min, stainless roller is pressed through the transparent graphene conductive film after doping treatment, and pressure is adjusted to 200psi, repeats twice.
The light transmittance of thus obtained transparent graphene conductive film is 80, and surface resistance is 330 Ω/.
Embodiment
5
:
A kind of with native graphite alkene for the stock roll processing procedure to rolling standby transparent graphene conductive film
(1) preparation of Graphene coating ink
Adding hydroxypropyl methyl cellulose mixing and stirring in the graphene platelet solution (concentration 1mg/ml) embodiment 1 prepared and form Graphene coating ink, finally, hydroxypropyl methyl cellulose accounts for the 1% of coating ink gross mass.
(2) preparation of adhesion layer coating liquid
Poly-methyl methacrylate vinegar (PMMA) is dispersed in dimethyl ether and is configured to the solution that weight concentration is 10 %.
(3) preparation of liquid crystalline polymer blends coating liquid
By epoxy resin, polyamide modified dose, epoxychloropropane (little molecular regulation refractive index) according to 4:1:3.2 ratio be in harmonious proportion, add the liquid crystal compound (LC-Beijing Bayi Space LCD Materials Technology Co., Ltd.) with identical refractive index of aforementioned substances gross mass 70%；And the glass fiber powder of 2000 a small amount of mesh, its a diameter of 6.5 μm, as dunnage, are sufficiently mixed stirring 3 hours under conditions of room temperature, are liquid crystal polymer coating liquid.
(4) coil coating is applied processing procedure by transparent graphene conductive film electrode roll.
Prepare production line signal as it is shown in fig. 7, can be applied by continuous print by transmitting path flexible substrate or process.Wind-up roll shaft 511 draws 120 μ m-thick, PET substrate 501 wide for 1m, moves along 53 directions from unreeling roll shaft 512, and the speed of service is 150mm/s.PET substrate to experience a series of coating process and processing procedure subsequently on 53 directions.
In pre-treatment working group 513, through Plasma process, process power is 150W, and the most coated module coating PMMA solution forms adhesion layer.Solvent volatilization is made to form adhesion layer 502 by 120 DEG C of heat treatments again after the coating of this adhesion layer.
Then enter Graphene/nano silver wire ink application job station 514, form Graphene/nano silver wire compound oil layer of ink 503 by slit extrusion coating module.503 layers of coated entrance dried work station 515, treatment temperature is 120 DEG C, a length of 30s during experience, thus forms Graphene/nano silver wire composite conductive layers 504.
Graphene conductive layer 504 will be carried out pressure treatment by pressure treatment roll shaft 517 and 518 further, strengthening the switching performance between graphene platelet and nano silver wire thus strengthen the electric conductivity of graphene conductive layer, additionally the smooth performance of graphene conductive layer also is able to strengthen.Control at 300mTorr at this working group's clamping pressure.
Afterwards, graphene conductive layer 504 enters reduction treatment work station (group) 519 and carries out also principle.504 layers will be soaked in the reduction treatment work station containing 55%HI acid solution, invade bubble 30s and carry out reduction treatment at 90 DEG C.Drying work station 520 processes, and treatment temperature is 180 DEG C, a length of 60s during experience.
Finally, transparent graphene conductive film electrode, mould release membrance laminating work station 521 is fitted protecting film, thus is reached the effect to electrode protection.So far transparent graphene conductive film electrode is formed.
Embodiment
7
:
Different size graphene platelet performance comparison is tested
It is understandable that, the viscosity of graphene dispersing solution, the cutting performance of dispersion liquid, interaction between the size of graphene platelet and graphene platelet, will affect and be coated in the switching performance each other of Graphene on PET substrate, and then affect light transmittance and the surface resistance of Graphene transparency conductive electrode.In this embodiment, it will contrast as a example by different size Graphene, the dimensional effect impact on Graphene transparency conductive electrode surface resistance is illustrated.
By in embodiment 1, the small size graphene solution separated, continuation, at 8000rpm, is centrifuged 5min clock, isolates small size 1 graphene platelet, and the average-size of its thin slice is 100 μm2, residual solution is demarcated as small size 2 graphene platelet, and the average-size of its thin slice is 50 μm2.Above two graphene platelet is modulated into the graphene dispersing solution that concentration is 0.5mg/ml.Two kinds of undersized graphene platelets, repeat to test in embodiment 2, and third step the most in example 2, coating speed all selects 10m/min to apply.And the undersized graphene platelet of latter two repeats to test in embodiment 3 completely.Final the data obtained contrast see table.It can be seen that the transparent conductive film prepared by big size graphene has less contact node, using the teaching of the invention it is possible to provide more excellent electric conductivity.
Embodiment
8
:
A kind of preparation of liquid crystal type light modulation film device
(1) by epoxy resin, polyamide modified dose, epoxychloropropane (little molecular regulation refractive index) according to 4:1:3.2 mass ratio be in harmonious proportion, add the liquid crystal compound (LC-Beijing Bayi Space LCD Materials Technology Co., Ltd.) with identical refractive index of aforementioned substances gross mass 70%, and the glass fiber powder of 2000 a small amount of mesh, a diameter of 6 μm are as dunnage, under conditions of room temperature, it is sufficiently mixed stirring 3 hours, is liquid crystal compound coating liquid.
(2) select the electrode in embodiment 3 as bottom electrode, liquid crystal compound is applied on the bottom electrode, and leave the region of 1.5cm as blank, not coated with liquid crystal mixture；And using another electrode in embodiment 4 as upper electrode, this malposition of electrode is placed on bottom electrode, afterwards by the liquid crystal compound that upper/lower electrode pressing extrusion is unnecessary, solidify 3 hours in the baking oven of 55 DEG C the most again；Dislocation zone being applied conductive silver paste, is placed in conductive silver paste by wire, form extraction electrode after 1h solidifies, thus prepared by device.
It should be noted that and understand, in the case of without departing from the spirit and scope of the present invention required by appended claims, it is possible to the present invention of foregoing detailed description is made various modifications and improvements.It is therefore desirable to the scope of the technical scheme of protection is not limited by given any specific exemplary teachings.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, but the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention has to rely on above-mentioned detailed process equipment and technological process could be implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within protection scope of the present invention and open scope.
Claims (18)
1. a flexible intelligent light modulation film device electrode material, it is characterized in that: described electrode material is the transparent conductive film being made up of native graphite alkene, this thin film is at least made up of graphene conductive layer and substrate layer, optional also comprises functional layer, and described intelligent dimming membrane module refers to electroluminescent light modulation film device based on liquid crystal material.
2. an electrode material as claimed in claim 1, it is characterized in that: the basic structure that described native graphite alkene refers to wherein Graphene be in nature through long-term Geological Evolution the graphene-structured of self-assembling formation, including graphene-structured present in native graphite, coal and/or oil.
3. a flexible intelligent light modulation film device electrode material as claimed in claim 1, described native graphite alkene preferred natural graphite.
4. a flexible intelligent light modulation film device electrode material as claimed in claim 1, described graphene conductive layer, it is characterised in that described graphene conductive layer is the graphene conductive layer sprawled on substrate by a large amount of native graphite alkene thin slices, stacked, be interconnected to form；Described graphene platelet is interconnected to form the connected mode of conductive layer and includes that a connection, line connect, face connects, three-dimensional connects or the mixing of aforementioned connected mode.
5. a flexible intelligent light modulation film device electrode material as claimed in claim 1, described functional layer is any one or more in protective layer, antireflection layer, anti-dazzle photosphere, barrier layer, tack coat.
6. a flexible intelligent light modulation film device electrode material as claimed in claim 1, described substrate layer is transparent flexible substrate layer, including Merlon, silica gel, polrvinyl chloride, polyethylene terephthalate, polystyrene, polymethylacrylic acid, glass resin, polypropylene, fluoropolymer, polyimides, polyamide, polyether-ether-ketone resin, polynorbornene, polyester, polyvinyl, acrylonitrile-butadiene-styrene copolymer, silica gel or the copolymer of above-mentioned polymer, mixture and combinations thereof.
7. a flexible intelligent light modulation film device electrode material as claimed in claim 1, described substrate layer is preferably polyethylene terephthalate (PET).
8. a flexible intelligent light modulation film device electrode material as claimed in claim 1, described transparent conductive film is 60-95% at 550 nm visible region light transmittances, and surface resistance is 0.2-30 K Ω/.
9. the preparation method of arbitrary flexible intelligent light modulation film device electrode material as described in claim 1-8, it is characterized in that with the material rich in native graphite alkene as raw material, chemical stripping method, physics stripping method or a combination thereof mode is used to be stripped out by grapheme material therein, form graphene dispersing solution, then graphene dispersing solution is coated with on flexible substrates.
10. a preparation method as claimed in claim 9, before painting work, described flexible substrate will be through pre-treatment；After painting work, in addition it is also necessary to through post processing.
11. 1 kinds of preparation methoies as described in claim 9 or 10, the described material rich in native graphite alkene include native graphite, coal, coal tar, black petroleum products one or more, one or more in the most natural flaky graphite or expanded graphite.
12. 1 kinds of preparation methoies as claimed in claim 9, described physics stripping method utilizes physical action to be eliminated by graphite layers active force in the case of main conjugated structure in not destroying graphite linings and obtains Graphene.
13. 1 kinds of preparation methoies as claimed in claim 9, described chemical stripping method utilizes chemical action to insert active substance in graphite layers thus eliminates graphite layers active force and obtain Graphene.
14. 1 kinds of preparation methoies as claimed in claim 9, the Graphene that described employing chemical stripping method, physics stripping method or a combination thereof mode are stripped out, the form of its Graphene includes the flawless Graphene in surface, the defective Graphene in surface, graphene oxide, chemical modification Graphene, functionalization graphene or the combination of foregoing graphites alkene.
15. 1 kinds of preparation methoies as claimed in claim 9, described coating process refers to can be used for the various wet coating processes of volume to volume coated technique, is coated with including spraying, blade coating, rod, nick coating, slot die coating, lip mould is extrusion coated and comma coating.
16. 1 kinds of preparation methoies as claimed in claim 10, described pre-treatment is heat treatment, physical cleaning, Chemical cleaning, UV ozone process, Plasma process, Corona discharge Treatment, pressure treatment, functional layer process or the combination of aforementioned any process.
17. a preparation method as claimed in claim 10, described post processing refers to the processing method improving graphene film electric conductivity further with light transmission, for doping treatment, reduction treatment, UV process, cured, electron beam treatment, radiation treatment, heat treatment, physical cleaning, Chemical cleaning, UV ozone process, Plasma process, Corona discharge Treatment, pressure treatment or the combination of aforementioned any process.
18. 1 kinds of application of arbitrary electrode material as described in claim 1-8, it is for providing a kind of novel transparent graphene conductive film window electrode with native graphite alkene as construction unit, and preparation is based on liquid crystal type intelligent dimming membrane module.
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