Summary of the invention:
For the deficiencies in the prior art part, the present invention proposes a kind of intelligent dimming membrane module based on Graphene transparency conductive electrode.This Graphene transparency conductive electrode by carbon containing organic macromolecule or/and macromolecule cracking is standby, its preparation technology is simple, rational in infrastructure, product yield is high, it is adaptable to all based on liquid crystal type, inorganic electrochromic type, organic electrochromic type intelligent dimming membrane module.
A kind of intelligent light modulation film, it is characterised in that set gradually from bottom to up: the first electrode unit of comprising transparent graphene conductive film, light regulon, the second electrode unit of comprising Graphene/inorganic matter compound transparent electricity conductive film;The transparent conductive film that described transparent graphene conductive film is made up of grapheme material, described Graphene is or/and macromolecule is prepared from for raw material with carbon containing organic macromolecule;Described first electrode unit and the second electrode unit shift to install, and dislocation distribution has extraction electrode;Described light regulon embeds dunnage to prevent the first electrode unit and the contact of the second electrode unit;Whole device is encapsulated by encapsulating material;Described dislocation is monolateral dislocation or bilateral dislocation.
Example intelligent dimming membrane module as shown in Figure 1, this intelligent light modulation film sets gradually from bottom to up: comprise the first electrode unit 10 of transparent graphene conductive film, light regulon 2, the second electrode unit 11 of comprising Graphene/inorganic matter compound transparent electricity conductive film.Preferably, first electrode unit and the second electrode unit can carry out dislocation and place, and is beneficial to the extraction of extraction electrode 41,42, and dislocation mode includes: monolateral dislocation or bilateral dislocation, Fig. 2 (a) just illustrates a kind of monolateral dislocation mode, and Fig. 2 (b) illustrates a kind of bilateral dislocation mode.Further, described light regulon needs mixed mat backing 5, to prevent the first electrode unit and the contact of the second electrode unit;Its shape of described dunnage mostly is spherical, and diameter is 2 ~ 100 microns, and its material can be Muscovitum microballon, glass microballoon, glass fibre, plastic particles and combination thereof.Further, described electrode is encapsulated by encapsulating material 3;Described encapsulating material is preferably epoxy glue.
Described carbon containing organic macromolecule is or/and macromolecule contains big π key, aromatic rings or hydridization aromatic ring structure.
Described carbon containing organic macromolecule is or/and contain layer structure in high molecular space structure;Layered structure, can by carbon containing organic macromolecule or/and high molecular side chain or main chain add sandwich compound structure, multilamellar phthalocyanine and derivant structure thereof and emerge from.
Described carbon containing organic macromolecule is or/and macromolecule is heterochain polymer, conducting polymer, amphipathic nature polyalcohol, liquid crystal polymer, carbochain polymer.
Described transparent graphene conductive film is multiple structure, and at least includes transparent substrates, graphene conductive layer.Further, described transparent graphene conductive film can comprise other functional layers, and functional layer may be located at below substrate, can also be positioned at above graphene conductive layer or its combination.Described functional layer be in reflecting layer, protective layer, antireflection layer, anti-dazzle photosphere, barrier layer, tack coat any one or multiple.In the embodiment of an indefiniteness, as it is shown on figure 3, transparent graphene conductive film electrode unit is by protective layer 11, substrate 12, tack coat 13, graphene conductive layer 14.
Described graphene conductive layer, it is characterised in that affiliated graphene conductive layer is to be made up of various grapheme materials tilings such as graphene platelet, Graphene monocrystalline, Graphene polycrystalline.The thickness of usual graphene conductive layer is 0.4 ~ 10nm.
Described transparent substrates, including flexible substrate, rigid substrate or its superposition.Being generally directed to the application of flexible, and be easy to the factors such as construction, operation, production, substrate is chosen as flexible substrate.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 and combination thereof.
Described light regulon is based on the critical function module of the intelligent light modulation film of Graphene/inorganic matter mixed electrode, including liquid crystal type light regulon, electrochromism light regulon and combination thereof.
Namely the mixed layer that described liquid crystal type light regulon has only to liquid crystal and polymer may be constructed the basic structure of this light regulon, and the optimal thickness of the mixed layer of liquid crystal and polymer is chosen as: 1 μm ~ 100 μm.
In actual embodiment, liquid crystal material and polymer need same refractive index, to ensure light transmission and the mist degree of whole nesa coating.It is difficult to due to single liquid crystal composition and refractive index polymer reaches good coupling, in the embodiment of some reality, the liquid crystal material selected is generally mixed crystal material, for instance select: the mixed crystal material of the models such as 5CB, 7CB, 5PCH, 7PCH, E7 of Merck KGaA.
Described electrochromism light regulon, at least includes the superposition of three-decker: ion storage, dielectric substrate, electrochromic layer;The preferred thickness of whole electrochromism type light regulon is 0.1 ~ 100 μm.
All layers of the light regulon being sandwiched between transparency conducting layer in electrochromic intelligent light modulation film all need have ion transmission, hole transport or electron transport property, in order to enable potential barrier and the carrier transmission characteristics of Graphene electrically conducting transparent unit and light regulon to be mutually matched, to realize effective linking of light regulon and graphene conductive layer in intelligent light modulation film.Electrochromism light regulon can also add one or more in potential barrier regulating course, transition zone, electronic barrier layer, hole blocking layer, cushion as optimized Structure Design, with the overall performance of Intelligent Optimal light modulation film.C60 such as can be selected in some embodiments as potential barrier regulating course.
Such as in the embodiment of an indefiniteness, as shown in Figure 4, this electrochromic cells includes potential barrier regulating course 221, ion storage 222, dielectric substrate 223, electrochromic layer 224, potential barrier regulating course 225 from top to bottom successively.
Described electrochromic layer includes organic electrochromic layers and inorganic electrochromic layer, electrochromic layer can also be the structure of organic and inorganic common mixing, the discoloration of electrochromic intelligent light modulation film is had particularly important impact by the thickness of electrochromic layer, and its thickness range of choice is 100nm ~ 30 μm.
The preparation method that another main purpose of the present invention is to provide a kind of intelligent dimming membrane module including Graphene transparency conductive electrode, its step includes:
(1) Graphene transparency conductive electrode is prepared.
(2) two the identical Graphene transparency conductive electrodes prepared according to step (1), as the first electrode unit and the second electrode unit.Select any one in the first electrode unit and the second electrode unit or two full choosings, at the electrode surface each layer in coating light regulon, it is necessary to one or two limit reserved does not apply on electrode.After then embedding dunnage glass microballoon on the surface being coated with light regulon again, the first electrode unit and the second electrode unit are carried out dislocation laminating.
(3) the device epoxy glue seal that will obtain in (2) step with encapsulating material.
(4) prepared by extraction electrode, does not namely apply the part of dimming unit in the position of dislocation and is coated with and applies silver and starch bonding external circuit wire, or direct conductive tape pastes foil, or divides in dislocation with the U-shaped thin slice clamping of metal and be carried out.
In the step (1) of described preparation method, its specific embodiment is, carbon containing organic molecule or macromolecule are treated to the dispersion liquid or slurry form that can apply, by this dispersion liquid that can apply or slurry coating on graphitization catalyst substrate, in catalyst substrate, one layer of uniform thin film is formed then through film forming after processing, and it is placed on inert atmosphere, high-temperature heat treatment is passed through under reducing atmosphere or vacuum state, the organic molecule in catalyst substrate and macromolecule is made to be cracked into graphene film layer, further the graphene film layer of acquisition is transferred to transparent substrates surface, form transparent graphene conductive film electrode.
In the detailed description of the invention of described preparation method step (1), in order to obtain electric conductivity and the more excellent graphene film of optical property, described carbon containing organic macromolecule is or/and macromolecule comprises in all structures the carbon containing organic macromolecule containing big π key, aromatic rings or hydridization aromatic rings or/and macromolecule.
In some embodiments, carbon containing organic macromolecule or/and macromolecule can and catalyst substrate surface action form coordinate bond so that catalyst surface can form carbon containing organic macromolecule or/and high molecular self-assembled film or absorption last layer organic molecule.Such as Fig. 5[1]Shown in, in figure, M represents metallic atom, and the nitrogen in the pyrrole group of polyvinylpyrrolidonemolecules molecules and the lone pair electrons on oxygen atom can form coordinate bond with metal surface atom, thus form thin film in metal surface.
In some embodiments, carbon containing organic macromolecule, or/and macromolecule can pass through hydrogen bond, Van der Waals force, hydrophobe effect, forms the single or multiple lift molecular film of self assembly on catalyst substrate surface.The number of plies of described self-assembled monolayers can control the number of plies of the standby Graphene of cracking.
In some embodiments, at described carbon containing organic macromolecule or/and high molecular space structure adds layer structure, with realization, the number of plies of graphene film can be controlled.Layered structure, can by carbon containing organic macromolecule or/and high molecular side chain or main chain add sandwich compound structure, multilamellar phthalocyanine and derivant structure thereof and emerge from.Such as Fig. 6[2]Shown a kind of multilamellar phthalocyanine structure just can be added in the side chain entering organic polymer or in main chain, the M in figure represents metallic atom.
In some embodiments, carbon containing organic macromolecule is or/and macromolecule can also be polymerized in catalyst substrate by little molecule.Such as catalyst substrate is soaked in the hydro-thermal reaction liquid entering glucose, catalyst substrate will form the carbonized polymers of one layer of glucose.
In some embodiments, carbon containing organic macromolecule is or/and macromolecule can also be chosen as heterochain polymer, conducting polymer, amphipathic nature polyalcohol, liquid crystal polymer, carbochain polymer.
In the detailed description of the invention of described preparation method step (1), described catalyst substrate material includes the simple substance of Ni, Co, Fe, Pt, Au, Al, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V and Zr, alloy or mixture.Its form of described catalyst substrate is deflection flexible metal foil or stiff sheet.In some embodiments, the form of substrate is preferably flexible metal foil.In some embodiments, Graphene needs to be transferred in the transparent substrates of rigidity, then its preferred catalyst substrate is generally stiff sheet.
In the detailed description of the invention of described preparation method step (1), wherein high-temperature heat treatment mode includes: induction heat, radiation heating, laser, infrared ray, microwave, plasma heating, ultraviolet, surface plasma heat.
In the detailed description of the invention of described preparation method step (1), described graphene film is transferred to the method for flexible substrate and includes but not limited to: substrate etching transfer method, electrochemistry transfer, dry method transfer, mechanical stripping transfer.In some embodiments it may be desirable to repeatedly shift to realize the higher electric conductivity of graphene conductive layer.
In the step (2) of described preparation method, described light regulon can be multilamellar can also be monolayer.Such as organic and inorganic electrochromic light regulon, its structure just includes at least: dielectric substrate, ion storage and electrochromic layer, in the embodiment of some reality, in addition it is also necessary to add potential barrier regulating course and electronic barrier layer etc..These multilamellars both can be coated in successively on an electrode unit and fit with another electrode unit, it is also possible to be coated in by the layer that above-mentioned needs apply on two electrode units respectively and fit.
In the step (2) of described preparation method, the interpolation of described dunnage, not merely it is limited to the method simply by spraying and dunnage is embedded in light regulating course.It is generally directed to the dimming unit of multiple structure, in order to not affect coating and the printing effect of each layer, it is common that again dunnage is sprayed at surface after being applied by each layer.And for the dimming unit of single layer structure, for instance for liquid crystal type dimming unit, it is possible to will be directly coated with after glass microballoon and liquid crystal, polymer mixed or print.
In the step of (1) of described preparation method ~ (4), in the preparation of related to layer or the preparation of extraction electrode, all adopt coating and printing process, be mainly coated with including but not limited to: nano impression, spin coating, spraying, blade coating, rod, nick coating, slot die coating, lip mould are extrusion coated, comma coating, silk screen printing, grenadine printing, inkjet printing etc..Preferably, coating method is chosen as that spraying, blade coating, rod paintings, slit extrusion coating, lip mould be extrusion coated, comma applies.Such as in this patent embodiment, in the conductive layer coating of Graphene/Organic substance compound, coating method is that rod is coated with, and its preferred coating speed is 10 ~ 1500mm/s.Further, coating speed is preferably 100 ~ 300mm/s.
Before arbitrarily coating or printing operation, the surface of required coating or printing, it is typically passed through a series of pre-treatment, surface described herein both can be initial substrates can also be the layer arbitrarily existed.These pretreatment process typically include, but not limited to: the combination of heat treatment, physically or chemically cleaning, UV ozone process, Plasma process, Corona discharge Treatment, pressure treatment or aforementioned processing.Such as: the PET substrate being directed to flexibility in this patent embodiment needs to first pass through before application aging heat treatment, then through cleaning treatment.Again such as: in this patent embodiment, on a pet film before coated graphite alkene/Organic substance composite coating liquid, it is possible to through Plasma process, to strengthen wellability.
After arbitrarily coating or printing operation, on the layer printed or apply, extraction electrode is typically passed through a series of post processing, and the mode of these post processings typically includes, but not limited to: the combination of 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 aforementioned processing.Such as, in this patent embodiment, the liquid crystal type light regulating course of coating needs through cured after pressing.
It is an advantage of the invention that first: select with carbon containing organic macromolecule or/and macromolecule can greatly reduce the electrode cost of intelligent light modulation film for transparent graphene conductive film prepared by raw material so that intelligent light modulation film can large-scale commercial;Second: the intelligent dimming membrane module that the present invention produces has flexibility, facilitates forms to construct;3rd: the present invention includes the structural design of the intelligent light modulation film device optimization of transparent graphene conductive film and achieves effective linking of light regulating course and graphene conductive layer in intelligent light modulation film.
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 some embodiments more specifically and the experimental result providing support for these embodiments.But, applicant is it is to be noted, that herein below for illustrative purposes only, but not is intended to limit the present invention in any manner scope of the claims.
Detailed description of the invention:
Preparation example 1:
A kind of with carbon containing organic macromolecule or/and the Graphene transparent conducting glass prepared for raw material of macromolecule
(1) configuration concentration is polyvinylpyrrolidone (PVP)/DMF (DMF) solution of 1.2g/ml.The Cu paper tinsel of 10cm*10cm is put in PVP/DMF solution, then this solution is heated to 120 DEG C, process Cu paper tinsel 1 hour at this temperature, one layer of PVP molecule will be adsorbed on Cu paper tinsel surface by coordinate bond.
(2) the Cu sheet ethanol obtained and deionized water are cleaned, wash the PVP molecule of excess surface, then process in 60 DEG C of baking ovens 2 hours again and dry.Acquisition Cu sheet is put in inert gas filled tube furnace, then furnace body temperature is increased to 800 DEG C, process 2 hours, so will form a layer graphene layer on the surface of copper sheet.Finally naturally cooled to room temperature.
(3) by the obtained Cu paper tinsel surface method by spin coating, with sol evenning machine under the rotating speed of 3600rad/s, the solution of 6% polymethyl methacrylate (PMMA) in spin coating.It is then placed in etching liquid (copper sulfate: hydrochloric acid: water=1:5:5) etching half an hour, namely can be transferred on the healthy and free from worry substrate of 10cm*10cm after copper etching.Graphene is transferred to after in glass substrate, places into 60 DEG C of process 20min in baking oven, is then placed in acetone and soaks, remove PMMA.Namely Graphene transparent conducting glass is obtained.
Preparation example 2:
A kind of with carbon containing organic macromolecule or/and the transparent graphene conductive film prepared for raw material of macromolecule
(1) configuration concentration is the PVP/ aqueous solution of 0.3g/ml.The Cu sheet of 3cm*3cm is put in PVP/ aqueous solution, then this solution is heated to 120 DEG C, process Cu paper tinsel 1 hour at this temperature, one layer of PVP molecule will be adsorbed on Cu paper tinsel surface by coordinate bond.
(2) the Cu sheet ethanol obtained and deionized water are cleaned, wash the PVP molecule of excess surface, then process in 60 DEG C of baking ovens 2 hours again and dry.Acquisition Cu sheet is put in inert gas filled tube furnace, then furnace body temperature is increased to 800 DEG C, process 2 hours, so will form a layer graphene layer on the surface of copper sheet.Finally naturally cooled to room temperature.
(3) by obtaining the Cu paper tinsel surface method by spin coating, with sol evenning machine under the rotating speed of 3600rad/s, the solution of 6% polymethyl methacrylate (PMMA) in spin coating.Graphene is stripped down by the electrochemistry bubbling stripping means of reference literature " ACSNano, 2011,5 (12): 9927 ~ 9933 ", and transfers them on flexible substrate PET.
Preparation example 3:
A kind of with carbon containing organic macromolecule or/and the transparent graphene conductive film prepared for raw material of macromolecule
(1) configuration concentration is the polyaniline/DMF solution of 0.3g/ml.The Cu sheet of 10cm*4cm is put in polyaniline/DMF solution, then this solution is heated to 120 DEG C, process Ni paper tinsel 1 hour at this temperature, will absorption one strata aniline molecule on Ni sheet surface.
(2) the Ni sheet ethanol obtained and deionized water are cleaned, wash the polyaniline molecule of excess surface, then process in 60 DEG C of baking ovens 2 hours again and dry.Acquisition Ni sheet is put in inert gas filled tube furnace, then furnace body temperature is increased to 800 DEG C, process 2 hours, so will form a layer graphene layer on the surface of Ni sheet.Finally naturally cooled to room temperature.
(3) with 12cm*4cmPET for substrate, successively soak respectively with deionized water, acetone and dry after cleaning 10 minutes in supersonic cleaning machine;PET is put into O2Plasma work station MarchPX250 process, setup parameter is 150W, 30 seconds, O2Air-flow: 80sccm, pressure: 350mTorr.The PET film surface handled well is utilized the epoxy resin that bar coating last layer is 1 micron thick, the one side then PET film being contained epoxy resin is pressed against the surface of Ni sheet, applying pressure is 150Kpa, owing to copper sheet is shorter two centimetres than PET, so there being the width of two centimetres not have epoxy resin.By PET/ epoxy resin/graphite alkene film/Ni sheet good for clamping, put into and the baking oven of 120 DEG C processes 2 hours so that epoxy glue solidifies.Then by PET from copper sheet sur-face peeling, it will obtain PET/ epoxy resin/graphite alkene membrane structure.