CN101611346B - Electrolyte material for electro-controlled device, method for making the same, electro-controlled device including the same and method for producing said device - Google Patents
Electrolyte material for electro-controlled device, method for making the same, electro-controlled device including the same and method for producing said device Download PDFInfo
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- CN101611346B CN101611346B CN2007800514639A CN200780051463A CN101611346B CN 101611346 B CN101611346 B CN 101611346B CN 2007800514639 A CN2007800514639 A CN 2007800514639A CN 200780051463 A CN200780051463 A CN 200780051463A CN 101611346 B CN101611346 B CN 101611346B
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- control gear
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F2001/164—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect the electrolyte is made of polymers
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Laminated Bodies (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention relates to an electrolyte material for an electro-controlled device, having variable optical/energetic properties, characterised in that it comprises a self-sustained polymer matrix containing ionic charges as well as a liquid for the solubilisation of said ionic charges, wherein the liquid does not solubilise said self-sustained polymer matrix, the matrix being selected so as to provide a percolation path for said ionic charges. The invention also relates to an electro-controlled device having variable optical/energetic properties and including such an electrolyte material, and to a method for producing such an electro-controlled device, characterised in that it comprises assembling the different layers thereof by calendaring or lamination and optionally under heating.
Description
But the present invention relates to the electrolyte of electric control gear, its preparation method, but comprise its electric control gear and make the method for said device.
But electric control gear like this is called as and has variable optics and/or energy characteristics.It can be generally defined as the lamination that comprises with lower floor:
-have first base material of glass function;
-have first conductive layer of the power lead-ining line of combination;
-electroactive system;
-have second conductive layer of the power lead-ining line of combination; With
-have second base material of glass function.
Electroactive system with multilayer comprises the two-layer electroactive material of being separated by electrolyte, and the electroactive material of said one deck at least in two-layer is electrochromic.Said therein two kinds of electroactive materials all are under the situation of electrochromic material, and they possibly be same or different.Therein one of electroactive material be electrochromic and another kind of be not under the electrochromic situation, the latter has the effect of counter electrode of colour developing and the colour killing process of participation system not.Under the effect of electric current, electrolytical ion filler be embedded in one of electrochromic material layer and break away from (d é sinserent) from another electrochromic material layer or from counter electrode thus obtain color contrast.
International Application PCT WO 2005/008326 has described the active system that obtains through following method, and said method is:
-get the matrix that gathers (ethylene oxide) film (being commonly referred to POE);
-make this matrix at monomer 3, expand in the 4-ethene dioxythiophene (EDOT);
-make the EDOT polymerization to obtain the POE film, be that electrochromic polymeric compounds gathers (3, the 4-ethene dioxythiophene) (PEDOT) on the two sides of this film;
-make the film of processing like this be dissolved in expansion in the solvent (like propylene carbonate) wherein at salt (like lithium perchlorate).
The advantage of this active system is to have certain mechanical strength, in other words, is (the autosupport é) of self-supporting.
Yet, be that the manufacturing of active system is complicated, therefore is difficult to industrial implementation like what can confirm.In addition, the contrast that can obtain, the i.e. ratio of the transmittance of the transmittance/colored state of colour killing state under the situation of two kinds of identical electrochromic materials; Almost be not satisfied; Usually quite approach 2, and this system is normally quite dark, even under the colour killing state; Transmittance usually is lower than 40%, or even 25%.
Therefore, the scheme that proposed of WO 2005/008326 is inappropriate for and replaces the current electrolytical scheme of use gelatine satisfactorily (referring to for example EP 0880189 B1; US 7038828 B2).
When the gelatine electrolyte is used for when electrolyte provides the purpose of certain intensity; For example polymer P EDOT, polyaniline or polypyrrole are introduced in electrochromic material between two-layer; Perhaps in " reservoir " zone between electrochromic material layer or the counter electrode layer; Discussed two-layer in each layer and conductive layer (like TCO, the english abbreviation of " transparent conductive oxide ") contact.The polymkeric substance that the gelatine electrolyte is mixed by the salt with solvent and dissolving, prepolymer (PMMA for example; POE) or monomer form; And but after in being placed in " reservoir " zone of electric control gear, it can for example be heated the polymerization of the crosslinked or monomer that causes polymkeric substance, prepolymer.
Except it is difficult for gel or solution (it is then by gelatine) are incorporated into the fact in the reservoir in industry, above-mentioned electrolyte is not a self-supporting.This scheme be unwell to use in the upright position with its medium under its deadweight effect in reservoir displacement possibly be large-sized device (like glass plate); Do not strengthen if said two base materials carry out enough machinery through periphery sealing, this makes in windowpane owing to causing that static pressure that windowpane " is heaved " causes the risk of opening.In addition, these electrolyte that are gel form comprise a large amount of solvents, and it is easy to interact with encapsulating material, and this causes and causes or promote the risk that two glass baseplates separate.
In order to solidify gelling; Can use the potpourri (referring to European patent application EP 1560064 A1 and International Application PCT WO 2004/085567 A2) that comprises polymer beads, solvent and salt; In a single day wherein said potpourri is placed in " reservoir " zone, is stood to heat to form transparent gel.This scheme can obtain to comprise the extremely viscous gel of less solvent.Yet, remain and be difficult to fill reservoir, and this system has mediocre light transmissive risk arranged, if when polymer beads does not have ideally dissolved and its refractive index to be different from the refractive index of remainder of gel.
Through International Application PCT WO 02/040578, the film of also known Pioloform, polyvinyl acetal such as polyvinyl butyral, it can play electrolyte and lamination embolus.Yet this product needed was formulated into electrolyte and was designed to especially before being shaped to the embolus form some electrochromic material (like Prussian blue or tungsten oxide) is produced effect.Since lack formulation flexibility, this product possibility validity much less, in addition incompatible with other electroactive material like for example PEDOT.
Attempting to solve in whole the problems referred to above processes; The applicant has proposed a kind of new and original scheme now; It is based on the self-supporting electrolyte system; Be suitable for giving good contrast performance and be easy to preparation and use, but and therefore be suitable for whole electric control gears, no matter its size is how.
But the object of the invention is the electrolyte that is used for electric control gear for having variable optics/energy characteristics therefore; It is characterized by it and comprise the self-supporting polymeric matrix; This matrix portion within it comprises ion filler (charges ioniques) and said ion dissolution of fillers liquid; Said liquid does not dissolve said self-supporting polymeric matrix; So that guarantee the percolation path of said ion filler, one or more polymkeric substance of selecting said polymeric matrix are can stand randomly lamination and the rolling condition under heating through selection for the latter.
According to electrolyte of the present invention transparent material advantageously.
The ion filler is by being dissolved at least a ion salt and/or at least a acid in the said liquid and/or being carried by said self-supporting polymeric matrix.
Dissolving liquid can be formed and/or be made up of at least a ionic liquid or fuse salt at ambient temperature by solvent or solvent mixture; Said a kind of ionic liquid or fuse salt or said different kinds of ions liquid or fuse salt constitute thus and carry ion dissolution of fillers liquid, and this ion filler has been represented all or part of ion filler that is comprised by said electrolyte.
Said one or more ion salt can be selected from lithium perchlorate, trifluoro-methanyl sulfonate or trifluoromethyl sulfonic acid, fluoroform sulfimide salt and ammonium salt.
Said one or more acid can be selected from sulfuric acid (H
2SO
4), trifluoromethane sulfonic acid (CF
3SO
3H), phosphoric acid (H
3PO
4) and polyphosphoric acid (H
N+2P
nO
3n+1).Said one or more ion salt and/or the concentration of one or more acid in solvent or solvent mixture are to be less than or equal to 5 mol especially, are preferably lower than or equal 2 mol and more preferably, are less than or equal to 1 mol.
Said solvent or said all kinds of solvents can be selected from boiling point and equal 95 ℃ at least, preferably equal those of 150 ℃ at least.
Said one or more solvents can be selected from dimethyl sulfoxide (DMSO), N; Dinethylformamide, DMAC N,N, propylene carbonate, ethylene carbonate, N-N-methyl-2-2-pyrrolidone N-(1-Methyl-2-Pyrrolidone), gamma-butyrolacton, glycols, alcohol, ketone, nitrile and water.
Said one or more ionic liquids can be selected from imidazole salts, like tetrafluoro boric acid 1-ethyl-3-methylimidazole (emim-BF
4), trifluoromethayl sulfonic acid 1-ethyl-3-methylimidazole (emim-CF
3SO
3), two (trifluoromethyl sulphonyl) imines (emim-N (CF of 1-ethyl-3-methylimidazole
3SO
2)
2Or emim-TSFI) and two (trifluoromethyl sulphonyl) imines (bmim-N (CF of 1-butyl-3-methylimidazole
3SO
2)
2Or bmim-TSFI).
The self-supporting polymeric matrix can be made up of at least one polymeric layer, in the infiltration fully of liquid described in this layer.
Can select said one or more matrix polymers and liquid so that the self-supporting active medium can stand to be equivalent in the lamination of back or the temperature of the required temperature of calendering step, promptly at least 80 ℃, at least 100 ℃ temperature especially.
Constitute the polymkeric substance of one deck at least and can be with atresia but the form of film that can in said liquid, expand exist all-or multipolymer.
Especially, the thickness of this film is lower than 1000 μ m, preferably 100-800 μ m and more preferably 100-700 μ m advantageously.
The polymkeric substance that constitutes one deck at least also be the porous membrane form all-or multipolymer; Said porous membrane randomly can expand in the liquid that comprises the ion filler, and the factor of porosity after selecting it to expand is so that allow ion filler seepage flow in the thickness of the film of liquid immersion.
So especially, the thickness of said film is lower than 1mm, is preferably lower than 1000 μ m, more preferably 100-800 μ m and more preferably 100-700 μ m.
Constituting at least, the polymeric material of one deck can be selected from:
-do not comprise the ion filler all-or multipolymer, said under these circumstances filler carries by the ion salt of at least a dissolving or acid and/or by at least a ionic liquid or fuse salt;
-comprise the ion filler all-or multipolymer, can improve the additional fillers of seepage flow speed under these circumstances and can carry by the ion salt of at least a dissolving or acid and/or by at least a ionic liquid or fuse salt; With
-at least a do not carry the ion filler all-or multipolymer and at least a comprise the ion filler all-or the potpourri of multipolymer, can improve the additional fillers of seepage flow speed under these circumstances and can carry by the ion salt of at least a dissolving or acid and/or by at least a ionic liquid or fuse salt.
Polymeric matrix possibly be made up of such film; Said film based on comprise the ion filler, be suitable for by itself obtain film all-or multipolymer (this film can guarantee the seepage flow speed of expectation or be higher than the seepage flow speed of expectation seepage flow speed basically for said ion filler); With based on comprise or do not comprise the ion filler, be suitable for by itself obtain film all-or multipolymer (but this film not necessarily allows to guarantee desired seepage flow speed can guarantee physical strength basically), regulate these two kinds all-or multipolymer in each content so that guarantee seepage flow speed and the physical strength that the self-supporting matrix of gained is desired simultaneously.
One or more polymkeric substance that do not comprise the polymeric matrix of ion filler can be selected from ethene, vinyl acetate and the multipolymer of at least a other comonomer randomly, like vinyl-vinyl acetate copolymer (EVA); Polyurethane (PU); Polyvinyl butyral (PVB); Polyimide (PI); Polyamide (PA); Polystyrene (PS); Gather (vinylidene fluoride) (PVDF); Polyethers-ether-ketone (PEEK); Gather (ethylene oxide) (POE); Chloropropylene oxide with gather (methyl methacrylate) multipolymer (PMMA).
Said polymkeric substance is selected from same train (famille), and no matter they are the prepare with porous or nonporous film, factor of porosity by film preparation during used pore-foaming agent provide.
As preferred polymkeric substance under the situation of nonporous film, can mention polyurethane (PU), or ethane-acetic acid ethyenyl ester (EVA) multipolymer.
As preferred polymkeric substance under the situation of porous membrane, can mention and gather (vinylidene fluoride).
One or more polymkeric substance or the polyelectrolyte that carry the polymeric matrix of ion filler can be selected from sulfonated polymer, and it has benefited from desired ion filler ion-exchange SO
3The H+ ion of H group, this ion-exchange comprising at polyelectrolyte expand in the liquid of ion filler before and/or carry out simultaneously with it.
Sulfonated polymer can be selected from the sulfonated copolymer of tetrafluoroethene, sulfonated polystyrene (PSS), and the sulfonated polystyrene multipolymer gathers (2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid) (PAMPS), sulfonated polyether-ether-ketone (PEEK) and sulfonated polyimide.
Self-supporting polymeric matrix or supporter can comprise the 1-3 layer.Especially, its thickness is lower than 1000 μ m, preferably 100-800 μ m and more preferably 100-700 μ m.
When this supporter comprises when two-layer at least, two-layer at least lamination can be made up of electrolyte and/or nonelectrolyte polymeric layer (before permeation liquid fully), expands with said liquid then.
When this supporter comprised 3 layers, two skins of lamination can be that the low bulk layer is that strong expanding layer is to help the seepage flow speed of ion filler with physical strength and the middle layer that helps said material.
Electrolyte according to the present invention advantageously has>=and 10
-4The conductivity of S/cm.
The self-supporting polymeric matrix can be through especially adding filler or inorganic nanoparticles, SiO especially with the ratio of a few percent of polymer quality in the supporter
2Nano particle carries out nano-structured.This can improve some performance such as the physical strength of said supporter.
The object of the invention also for preparing the as above method of defined electrolyte, is characterized by and makes polymer beads and solvent, if hope preparation porous polymer matrix; Also mix pore-foaming agent, the preparation of gained is poured on the supporter, and after solvent evaporation; Remove pore-foaming agent through washing in suitable solvent; For example, if during above-mentioned solvent evaporation, do not remove said pore-foaming agent, with the self-supporting film taking-up of gained; The dissolving liquid of electricity consumption active system soaks into said film then, carries out discharge opeing in case of necessity.
Can in 2 minutes-3 hours time period, immerse.Can under heating, for example under 40-80 ℃ temperature, immerse.
Can also apply ultrasound wave and immerse so that assist in dissolving liquid infiltrates through matrix.
The object of the invention is characterized by it and is made up of following also for to be used to prepare the as above kit of defined electroactive material:
-as above defined self-supporting polymeric matrix; With
-as above defined ion dissolution of fillers liquid, wherein said ion filler is dissolved.
But the invention still further relates to the electric control gear with variable optics/energy characteristics, it comprises as above defined electrolyte.
Especially, but said electric control gear comprises the layer of following series:
-have first base material of glass function;
-have first conductive layer of the power lead-ining line (une amen é e de courant associ é e) of combination;
-the first electroactive material layer, the reservoir of ion filler, it is in response to electric current;
-said electrolyte;
-the second electroactive material layer, the reservoir of ion filler, it is in response to electric current;
-have second conductive layer of the power lead-ining line of combination; With
-have second base material of glass function,
One deck at least in said two electroactive material layer is electrochromic; It can change color in the function of current; The ion filler of electrolyte is embedded in one of electroactive material layer and with another electroactive material layer and breaks away from; When applying electric current, to obtain two color contrasts between the electroactive material layer.
Base material with glass function is selected from glass (like float glass etc.) and transparent polymkeric substance especially; As gather (methyl methacrylate) (PMMA); Polycarbonate (PC), polyethylene terephthalate (PET), PEN (PEN) and cyclic olefine copolymer (COC).
Conductive layer is the metal types layer in particular, like the layer of silver, gold, platinum and copper; Perhaps transparent conductive oxide (TCO) layer is like the indium oxide (In of doped tin
2O
3: Sn or ITO), the indium oxide (In of antimony dopant
2O
3: Sb), the tin oxide (SnO of doped with fluorine
2: F) with the layer of the zinc paste (ZnO:Al) of adulterated al; The perhaps multilayer of TCO/ metal/TCO type, said TCO and metal are selected from top listed those especially; The perhaps multilayer of NiCr/ metal/NiCr type, metal are selected from top listed those especially.
When electrochromic system was used for carrying out work with transmission mode, the oxide that electronic conductive material is normally transparent, its electronic conduction were through mixing like In
2O
3: Sn, In
2O
3: Sb, ZnO:Al or SnO
2: F amplifies.Owing to its high electronic conductivity and its low light absorption, often comprise the indium oxide (In of doped tin
2O
3: Sn or ITO).When system was used for carrying out work with the reflection mode, one of electronic conductive material can be a metal.
Said two electroactive material layer can be identical electrochromic material layers.These two electrochromic electroactive material layer can be different, have complementary colour developing especially, its one of be anode colour developing (coloration anodique), and another is negative electrode colour developing (colorationcathodique).According to another possibility, one of electroactive material layer is an electrochromic layer, and another electroactive material layer is not electrochromic, only plays the reservoir or the counter electrode of ion filler.
Said one or more electrochromic materials especially can be selected from:
(1) inorganic electrochromic material, like the oxide of following metal: tungsten, nickel, iridium, niobium, tin, bismuth, vanadium, nickel, antimony and tantalum, individually or with the form of its two or more potpourri; In case of necessity, with the form of the potpourri of at least a additional metals such as titanium, tantalum or rhenium;
(2) organic electrochromic material is like electronic conductive polymer, like the derivant of polythiophene, polypyrrole or polyaniline;
(3) complex compound is as Prussian blue;
(4) metal-containing polymer (metallopolymers);
The combination of (5) at least two kinds of electrochromic materials of in (1)-(4), selecting at least two types.
One of electrochromic material the most widely-used and further investigation is a tungsten oxide, and according to the state that its filler embeds, it becomes transparent colour developing from the blueness colour developing.Electrochromic material with negative electrode colour developing, promptly its colored state is corresponding to embedding (or reduction) state and its colour killing state corresponding to breaking away from (or oxidation) state.In structure has five layers electrochromic system process, usually it is combined with the electrochromic material (like nickel oxide or yttrium oxide) with anode colour developing, its mechanism that develops the color is complementary.The optical contrast ratio of system is enhanced thus.All above-mentioned material is inorganic; But it can also combine with following: the inorganic electrochromic material of complex compound; Like Prussian blue or metal-containing polymer (metallopolymers); Perhaps even organic material such as electronic conductive polymer (derivants of polythiophene, polypyrrole or polyaniline etc.), even only use a type in these materials.
Non-electrochromic electroactive material can be a material optically neutral in related oxidation state, and like vanadium oxide, counter electrode can also be made up of silver-colored thin layer or carbon thin layer (high conductivity).In order to increase its transparency, these materials can carry out nano-structured.
But electric control gear of the present invention is configured to formation especially:
-be used for the roof of automobile, can be self-activating, perhaps be used for side window or the rear window or the rearview mirror of automobile;
The windshield of-automobile, aircraft or boats and ships or the part of windshield, car roof;
-aircraft porthole;
-be used for the display board of figure and/or alphanumeric information;
The glass plate of the indoor or outdoors of-buildings;
-skylight;
-show cabinet, display rack;
-be used for the cover glass plate of the object of picture class;
-computing machine anti-dazzling screen;
-glass furniture;
Partition wall between two rooms in-buildings.
But electric control gear carries out work with transmission mode or with the reflection mode.
Base material can be transparent, the plane or convex surface, and is bright or main body is painted, opaque or lighttight, has polygon or part curve shape at least.In the base material at least one can comprise another kind of function, like sunlight control, antireflection or automatic cleaning function.
But the invention still further relates to the as above method of defined electric control gear of manufacturing, it is characterized by the different layers of forming it and assemble through calendering or the lamination under heating randomly.
But said therein electric control gear is used to constitute under the situation of glass plate, and said method also comprises said different layers is assemblied in list or the multiple-glazing unit.
The present invention relates to list or compound glass plate at last, comprises as above defined electric control gear but it is characterized by it.
But following examples illustrate the present invention do not limit its scope.In these embodiment, abbreviation below using.
-PU: polyurethane
-CP: propylene carbonate
-EVA: vinyl-vinyl acetate copolymer
-NMP:N-N-methyl-2-2-pyrrolidone N-
-PEDOT: gather (3, the 4-ethene dioxythiophene)
-PSS: polystyrolsulfon acid ester
-PVDF: gather (vinylidene fluoride)
The PEDOT/PSS that is used for embodiment is sold with trade name
by Bayer company.
Use PU resin or PU film, it is sold by Huntsman, Argotec, Noveon, Polymar, Deerfield Urethane or Stevens Urethane company.
Use eva film, it is sold by Bridgestone, Dupont, Takemeruto, Sekisui, Tosoh company.
Use the PVDF powder, it is sold with trade name
or
by Arkema company.
The glass that is used for these embodiment is to be equipped with to have SnO
2: the glass of the conductive layer of F or ITO.
Gather (ethylene oxide) that be used for Comparative Examples sold with trade name
by Dai Ichi Kogyo Seiyaku.
Embodiment 1: prepare self-supporting electrolytic thin-membrane of the present invention
In order to verify that CP can make the PU film of 100 micron thick expand, and carries out bloating test.Five the PU samples of weighing in advance were dipped in it among CP 1 hour at 20 ℃ then.At last, after simple discharge opeing, and after using the paper wiping, and then the film of weighing.The weight that the measurement that the film of simple discharge opeing is carried out demonstrates 62%-68% increases.The weight that the measurement that the film of wiping is carried out demonstrates 18%-21% increases.Therefore be clear that CP not only is adsorbed onto on the PU surface, and be penetrated in the film dearly.
Through 5 * 5cm with 100 micron thick
2Square PU thin film dipped in the CP of the lithium perchlorate that contains 0.5M solution, obtained the self-supporting electrolytic thin-membrane.
After 1 hour, from the CP solution of lithium perchlorate, take out the self-supporting electrolytic thin-membrane at 20 ℃ of dippings, carry out discharge opeing then.
Embodiment 2: prepare self-supporting electrolytic thin-membrane of the present invention
Under the elementary stream effect, this film and glass plate are broken away from.After the drying, the thickness of film is about 40 microns.
Also in the CP of the lithium perchlorate that contains 0.5M solution, flooded 5 minutes subsequently in 30 minutes with ether washing PVDF film then.
Embodiment 3: prepare self-supporting electrolytic thin-membrane of the present invention
In order to verify that NMP can make the eva film of 200 micron thick expand, and carries out bloating test.Five the EVA samples of weighing in advance were dipped in it among NMP 1 hour at 20 ℃ then.Subsequently, after simple discharge opeing, and after using the paper wiping, the film of weighing again.The weight that the measurement that the film of simple discharge opeing is carried out demonstrates 70%-78% increases.The weight that the measurement that the film of wiping is carried out demonstrates 41%-42% increases.Therefore be clear that NMP not only is adsorbed onto on the EVA surface, and be penetrated in the film dearly.
Through 5 * 5cm with 200 micron thick
2Square eva film be immersed in the nmp solution that contains the 0.25M lithium perchlorate, obtained the self-supporting electrolytic thin-membrane.
After 1 hour, from the nmp solution of lithium perchlorate, take out the self-supporting electrolytic thin-membrane at 20 ℃ of dippings, carry out discharge opeing then.
Embodiment 4: manufacturing has the electrolytic thin-membrane of embodiment 1 and the electric driven color-changing part of PEDOT/PSS (cellule é lectrochrome)
Then, use the self-supporting electrolyte thin film preparation electric driven color-changing part of embodiment 1.Two PEDOT/PSS sediments have been obtained through being poured on the two K-glass glass (verres K-glass).
In case the PEDOT/PSS sediment is dry, one of two plates are attenuate (r é duited) in the acetonitrile solution of the lithium perchlorate that contains 1M.At attenuate (r é duction) afterwards, it is dry with washing with alcohol and blowing to be coated with the K-glass glass of (r é duced) PEDOT/PSS layer of attenuate.
The electrolytic thin-membrane of just having arranged liquid is deposited on the K-glass glass (the not plate of attenuate) that is coated with PEDOT/PSS then.Double-sided adhesive is arranged in around the electrolyte.At last, the K-glass glass that is coated with the PEDOT/PSS of attenuate is placed on the electrolytic thin-membrane then, so that accomplish element.
Element carries out autoclaving (autoclav é e) at 95 ℃ then, and the periphery of electric driven color-changing part centers on epoxy adhesive, and it plays encapsulation and is used for strengthening the cohesive force between two glass baseplates and the electrolytic thin-membrane.
Electric driven color-changing part transmittance at the colour killing state when short circuit of so making is 37%, and is 19% after 2 minutes under 2V.
Embodiment 5: manufacturing has the electrolytic thin-membrane of embodiment 2 and the electric driven color-changing part of PEDOT/PSS
Use the self-supporting electrolytic thin-membrane of embodiment 2 and the same program of following fully described in embodiment 4 to prepare electric driven color-changing part.
Electric driven color-changing part transmittance at the colour killing state when short circuit of so making is 38%, and is 19% after 2 minutes under 2V.
Embodiment 6 (Comparative Examples): manufacturing has based on the electrolyte of gel and the electric driven color-changing part of PEDOT/PSS
For relatively, follow said method but use polymeric gel type electrolyte to make electric driven color-changing part.
In this element, electrolyte is a gel, its comprise 60 weight % based on the resin that gathers (ethylene oxide), two (trifluoromethyl sulphonyl) imines lithiums of two (trifluoromethyl sulphonyl) imines of 1-ethyl-3-methylimidazole of 36 weight % and 4 weight %.Use oil spout lacquer film device deposits this gel with 100 microns thickness.
Electric driven color-changing part transmittance at the colour killing state when short circuit of making thus is 31%, and is 20% after 2 minutes under 2V.
Embodiment 7: manufacturing has the electrolytic thin-membrane of embodiment 1 and the electric driven color-changing part of inorganic electrochromic layer
Then, use the self-supporting electrolyte thin film preparation electric driven color-changing part of embodiment 1.Electrochromic layer and counter electrode layer are respectively the layers through tungsten oxide that obtains at the magnetron sputtering on glass that is coated with the ITO conductive layer and yttrium oxide.
The electrolytic thin-membrane of just having arranged liquid is deposited on one of said two base materials then.Use another base material to seal then with the element sealing and with double-sided adhesive.
Element carries out hot-pressing processing at 95 ℃ then, and the periphery of electric driven color-changing part centers on epoxy adhesive, and it plays encapsulation and can strengthen the cohesive force between two glass baseplates and the electrolytic thin-membrane.
The electric driven color-changing part of making thus under 1V after 2 minutes the transmittance at the colour killing state be 55%, and under-1.5V, be 24% after 2 minutes.
Embodiment 8: manufacturing has the electrolytic thin-membrane of embodiment 3 and the electric driven color-changing part of PEDOT/PSS
Then, use the self-supporting electrolyte thin film preparation electric driven color-changing part of embodiment 3.Prepare two PEDOT/PSS sedimentary deposits and described in embodiment 4, use.The electrolytic thin-membrane of just having arranged liquid is deposited on the K-glass glass (the not plate of attenuate) that is coated with PEDOT/PSS.Then double-sided adhesive is deposited on around the electrolyte, the K-glass glass that is coated with the PEDOT/PSS layer of attenuate is placed on the electrolytic thin-membrane, so that accomplish element.
Element is heated to 80 ℃ then, and the periphery of electric driven color-changing part centers on epoxy adhesive, and it plays encapsulation and can strengthen the cohesive force between two glass baseplates and the electrolytic thin-membrane.
Electric driven color-changing part transmittance at the colour killing state when short circuit of so making is 40%, and under 2V 2 minutes be later on 25%.
Claims (55)
1. but the electrolyte that is used for electric control gear that has variable optics/energy characteristics; It is characterized by it and comprise the self-supporting polymeric matrix; This matrix portion within it comprises ion filler and said ion dissolution of fillers liquid; Said liquid does not dissolve said self-supporting polymeric matrix, so that guarantee the percolation path of said ion filler, one or more polymkeric substance of selective polymer matrix are can stand randomly lamination and the rolling condition under heating through selection for this self-supporting polymeric matrix.
2. the electrolyte of claim 1 is characterized by said ion filler by being dissolved at least a ion salt and/or at least a acid in the said liquid and/or being carried by said self-supporting polymeric matrix.
3. each electrolyte in the claim 1 and 2; It is characterized by dissolving liquid forms by solvent or solvent mixture and/or by at least a ionic liquid or at the fuse salt of environment temperature; Said ionic liquid or fuse salt or said different kinds of ions liquid or fuse salt constitute thus and carry ion dissolution of fillers liquid, and this ion filler has been represented all or part of ion filler that is comprised by said electrolyte.
4. the electrolyte of claim 2 is characterized by said one or more ion salt and is selected from lithium perchlorate, trifluoro-methanyl sulfonate or trifluoromethyl sulfonic acid, fluoroform sulfimide salt and ammonium salt.
5. the electrolyte of claim 2 is characterized by said one or more acid and is selected from sulfuric acid (H
2SO
4), trifluoromethane sulfonic acid (CF
3SO
3H), phosphoric acid (H
3PO
4) and polyphosphoric acid (H
N+2P
nO
3n+1).
6. the electrolyte of claim 3; It is characterized by said one or more solvents and be selected from dimethyl sulfoxide (DMSO), N; Dinethylformamide, DMAC N,N, propylene carbonate, ethylene carbonate, N-N-methyl-2-2-pyrrolidone N-(1-Methyl-2-Pyrrolidone), gamma-butyrolacton, glycols, alcohol, ketone, nitrile and water.
7. the electrolyte of claim 3 is characterized by said one or more ionic liquids and is selected from imidazoles
salt.
8. according to the electrolyte of claim 7, it is characterized by imidazoles
Salt is tetrafluoro boric acid 1-ethyl-3-methylimidazole
(emim-BF4), trifluoromethayl sulfonic acid 1-ethyl-3-methylimidazole
(emim-CF
3SO
3), 1-ethyl-3-methylimidazole
Two (trifluoromethyl sulphonyl) imines (emim-N (CF
3SO
2)
2Or emim-TSFI) and 1-butyl-3-methylimidazole
Two (trifluoromethyl sulphonyl) imines (bmim-N (CF
3SO
2)
2Or bmim-TSFI).
9. claim 1 or 2 electrolyte is characterized by the self-supporting polymeric matrix and are made up of at least one polymeric layer, in the infiltration fully of liquid described in this polymeric layer.
10. the electrolyte of claim 9, it is characterized by constitute the polymkeric substance of one deck at least be atresia but the form of film that can in said liquid, expand all-or multipolymer.
11. the electrolyte of claim 9; It is characterized by constitute the polymkeric substance of one deck at least be the porous membrane form all-or multipolymer; Said porous membrane randomly expands in the liquid that comprises the ion filler, selects its factor of porosity after expansion so that allow ion filler seepage flow in the thickness of the film of liquid immersion.
12. the electrolyte of claim 9 is characterized by and constitutes at least that the polymeric material of one deck is selected from:
-do not comprise the ion filler all-or multipolymer, said under these circumstances filler carries by the ion salt of at least a dissolving or acid and/or by at least a ionic liquid or fuse salt;
-comprise the ion filler all-or multipolymer, the additional fillers that is used to improve seepage flow speed under these circumstances can be carried by the ion salt of at least a dissolving or acid and/or by at least a ionic liquid or fuse salt; With
-at least a do not carry the ion filler all-or multipolymer and at least a comprise the ion filler all-or the potpourri of multipolymer, the additional fillers that is used to improve seepage flow speed under these circumstances can be carried by the ion salt of at least a dissolving or acid and/or by at least a ionic liquid or fuse salt.
13. the electrolyte of claim 1 or 2; It is characterized by the self-supporting polymeric matrix is made up of such film; Said film based on comprise the ion filler, be suitable for by itself obtaining basically and can guaranteeing desired seepage flow speed or be higher than equal-or the multipolymer of film of the seepage flow speed of this expectation seepage flow speed for said ion filler; With based on comprise or do not comprise the ion filler, be suitable for by itself obtain not necessarily can to guarantee desired seepage flow speed but can guarantee basically physical strength film all-or multipolymer, regulate these two kinds all-or multipolymer in each content so that guarantee the seepage flow speed and the physical strength of expectation of the self-supporting matrix of gained simultaneously.
14. the electrolyte of claim 13 is characterized by the multipolymer that does not comprise the ion filler and is selected from ethene, vinyl acetate and the multipolymer of at least a other comonomer randomly.
15. the electrolyte of claim 14, it is characterized by said multipolymer is vinyl-vinyl acetate copolymer (EVA); Polyurethane (PU); Polyvinyl butyral (PVB); Polyimide (PI); Polyamide (PA); Polystyrene (PS); PVDF (PVDF); Polyethers-ether-ketone (PEEK); Polyoxyethylene (POE); The multipolymer of chloropropylene oxide and polymethylmethacrylate (PMMA).
16. the electrolyte of claim 1 or 2, said one or more polymkeric substance that it is characterized by the self-supporting polymeric matrix that carries the ion filler are selected from sulfonated polymer, and it has received the ion-exchange SO with desirable ion filler
3The H+ ion of H group, this ion-exchange comprising at said one or more polymkeric substance expand in the liquid of ion filler before and/or carry out simultaneously with it.
17. the electrolyte of claim 16, it is characterized by sulfonated copolymer, sulfonated polystyrene (PSS), sulfonated polystyrene multipolymer that sulfonated polymer is selected from tetrafluoroethene, gather (2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid) (PAMPS), sulfonated polyether-ether-ketone (PEEK) and sulfonated polyimide.
18. the electrolyte of claim 1 or 2 is characterized by the self-supporting polymeric matrix and comprises the 1-3 layer.
19. the electrolyte of claim 1 or 2; Wherein the self-supporting polymeric matrix comprises two-layer at least; It is characterized by two-layer at least lamination and before having permeated liquid fully, constitute, expand with said liquid then by electrolyte and/or nonelectrolyte polymeric layer.
20. the electrolyte of claim 1 or 2; Wherein the self-supporting polymeric matrix comprises 3 layers, and two skins that it is characterized by said lamination are that the low bulk layer is strong expanding layer so that help the seepage flow speed of ion filler so that help the physical strength and the middle layer of said material.
21. the electrolyte of claim 1 or 2, the thickness that it is characterized by the self-supporting polymeric matrix is lower than 1000 μ m.
22. the electrolyte of claim 1 or 2, the thickness that it is characterized by the self-supporting polymeric matrix are 100-800 μ m.
23. the electrolyte of claim 1 or 2, the thickness that it is characterized by the self-supporting polymeric matrix are 100-700 μ m.
24. the electrolyte of claim 1 or 2 is characterized by its conductivity>=10
-4S/cm.
25. the electrolyte of claim 1 or 2 is characterized by the self-supporting polymeric matrix and carries out nano-structured through adding the filler nanometer particle.
26. the electrolyte of claim 1 or 2 is characterized by the self-supporting polymeric matrix and carries out nano-structured through adding inorganic nanoparticles.
27. each electrolyte in claim 1 or 2 is characterized by the self-supporting polymeric matrix through adding SiO
2Nano particle carries out nano-structured.
28. the preparation method like each defined electrolyte in claim 1-27 is characterized by and makes polymer beads and solvent, if hope preparation porous polymer matrix; Also mix pore-foaming agent; The preparation of gained is poured on the supporter, and after solvent evaporation, removes pore-foaming agent through washing in suitable solvent; If during above-mentioned solvent evaporation, do not remove said pore-foaming agent; The self-supporting film of gained is taken out, soak into said film with said ion dissolution of fillers liquid then, randomly carry out discharge opeing.
29. be used for making kit, it is characterized by it and form by following as at each defined electrolyte of claim 1-27:
-like each defined self-supporting polymeric matrix in claim 9-27; With
-as at the defined ion dissolution of fillers of claim 3 liquid, wherein said ion filler is dissolved.
30. but, be included in each defined electrolyte among the claim 1-27 have the electric control gear of variable optics/energy characteristics.
But 31. the electric control gear of claim 30 is characterized by the layer that it comprises following series:
-have first base material of glass function;
-have first conductive layer of the power lead-ining line of combination;
-the first electroactive material layer, the reservoir of ion filler, it is in response to electric current;
-said electrolyte;
-the second electroactive material layer, the reservoir of ion filler, it is in response to electric current;
-have second conductive layer of the power lead-ining line of combination; With
-have second base material of glass function,
One deck at least in electroactive material two-layer is electrochromic; It can change color in the function of current; And when applying electric current; The ion filler of electrolyte is embedded in one of said electroactive material layer and with another electroactive material layer and breaks away from, to obtain two color contrasts between the electroactive material layer.
32. but the electric control gear of claim 31 is characterized by the base material with glass function and is selected from glass and transparent polymer.
But 33. the electric control gear of claim 32, it is characterized by said transparent polymer is polymethylmethacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), PEN (PEN) and cyclic olefine copolymer (COC).
But 34. each electric control gear in the claim 31 and 32, it is characterized by said conductive layer is the metal types layer; Perhaps transparent conductive oxide (TCO) type layer; The perhaps multilayer of TCO/ metal/TCO type; The perhaps multilayer of NiCr/ metal/NiCr type.
35. but the electric control gear of claim 34 is characterized by the layer of said metal types layer for silver, gold, platinum and copper.
But 36. the electric control gear of claim 34, it is characterized by said transparent conductive oxide (TCO) type layer is the indium oxide (In of doped tin
2O
3: Sn or ITO), the indium oxide (In of antimony dopant
2O
3: Sb), the tin oxide (SnO of doped with fluorine
2: F) with the layer of the zinc paste (ZnO:Al) of adulterated al.
But 37. the electric control gear of claim 31 or 32, it is characterized by said two electroactive material layer is identical electrochromic material layers.
But 38. the electric control gear of claim 31 or 32, it is different it is characterized by said two electrochromism electroactive material layer.
39. but the electric control gear of claim 38 is characterized by said two electrochromism electroactive material layer and is complementary colour developing, and be the anode colour developing one of in them, and another is the negative electrode colour developing.
But 40. the electric control gear of claim 31 or 32, it is characterized by one of said electroactive material layer is electrochromic layer, and another electroactive material layer is not electrochromic, only plays the reservoir or the counter electrode of ion filler.
But 41. the electric control gear of claim 31 or 32 is characterized by one or more electrochromic materials and is selected from:
(1) inorganic electrochromic material;
(2) organic electrochromic material;
(3) complex compound;
(4) metal-containing polymer;
The combination of (5) at least two kinds of electrochromic materials of in (1)-(4), selecting at least two types.
42. but the electric control gear of claim 41 is characterized by the oxide that said inorganic electrochromic material is following metal: tungsten, nickel, iridium, niobium, tin, bismuth, vanadium, nickel, antimony and tantalum, individually or with the form of its two or more potpourri; Randomly with the form of the potpourri of at least a additional metals.
43. but the electric control gear of claim 42, it is characterized by said at least a additional metals is titanium, tantalum or rhenium.
44. but the electric control gear of claim 41, it is characterized by said organic electrochromic material is electronic conductive polymer.
45. but the electric control gear of claim 44 is characterized by the derivant that said electronic conductive polymer is polythiophene, polypyrrole or polyaniline.
But 46. the electric control gear of claim 40; It is characterized by non-electrochromic electroactive material is material optically neutral in related oxidation state; Said counter electrode also randomly is made up of the silver-colored thin layer or the carbon thin layer of special conduction, these materials randomly by nano-structured so that increase its transparency.
47. but the electric control gear of claim 46, it is characterized by material optically neutral in the said oxidation state is vanadium oxide.
48. but the electric control gear of claim 31 or 32 is characterized by it and is configured to form:
-be used for the roof of automobile, can be self-activating, perhaps be used for side window or the rear window or the rearview mirror of automobile;
The windshield of-automobile, aircraft or boats and ships or the part of windshield, car roof;
-aircraft porthole;
-be used for the display board of figure and/or alphanumeric information;
-be used for the glass plate of the indoor or outdoors of buildings;
-skylight;
The show cabinet in-shop, display rack;
-be used for the cover glass plate of the object of picture class;
-computing machine anti-dazzling screen;
-glass furniture;
Partition wall between two rooms in-buildings.
49. but the electric control gear of claim 31 or 32 is characterized by it and carries out work with transmission mode or with the reflection mode.
50. but the electric control gear of claim 31 or 32, it is characterized by said base material is convex surface transparent flat or transparent, bright or main body is painted, opaque or opacification, has polygon or part curve shape at least.
51. but the electric control gear of claim 31 or 32, at least one that it is characterized by in the said base material comprises that being selected from sunlight controls the function of antireflection or automatic cleaning function.
52. but the electric control gear of claim 41, it is Prussian blue it is characterized by said complex compound.
But 53. make as in claim 31-52 the method for each defined electric control gear, it is characterized by the different layers of forming it and assemble through calendering or the lamination under heating randomly.
54. the method for claim 53, but wherein said electric control gear is used to constitute glass plate, it is characterized by with the form of list or compound glass plate said different layers is installed.
55. list or compound glass plate comprise as at claim 31 or 32 defined electric control gears but it is characterized by it.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0655610 | 2006-12-18 | ||
| FR0655610A FR2910137B1 (en) | 2006-12-18 | 2006-12-18 | ELECTRO-CONTROLLABLE DEVICE ELECTROLYTE MATERIAL, MANUFACTURING METHOD THEREOF, ELECTRO-CONTROLLABLE DEVICE COMPRISING SAME, AND METHOD OF MANUFACTURING THE SAME |
| FR0755985A FR2910138B1 (en) | 2006-12-18 | 2007-06-25 | ELECTRO-CONTROLLABLE DEVICE ELECTROLYTE MATERIAL, MANUFACTURING METHOD THEREOF, ELECTRO-CONTROLLABLE DEVICE COMPRISING SAME, AND METHOD OF MANUFACTURING THE SAME |
| FR0755985 | 2007-06-25 | ||
| PCT/FR2007/052553 WO2008084168A2 (en) | 2006-12-18 | 2007-12-18 | Electrolyte material for electro-controlled device method for making the same, electro-controlled device including the same and method for producing said device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101611346A CN101611346A (en) | 2009-12-23 |
| CN101611346B true CN101611346B (en) | 2012-04-25 |
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ID=38266695
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|---|---|---|---|
| CN2007800514639A Expired - Fee Related CN101611346B (en) | 2006-12-18 | 2007-12-18 | Electrolyte material for electro-controlled device, method for making the same, electro-controlled device including the same and method for producing said device |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101611346B (en) |
| FR (1) | FR2910137B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009130316A1 (en) | 2008-04-24 | 2009-10-29 | Chromogenics Ab | Electrolytes for electrochromic devices |
| FR2956754B1 (en) * | 2010-02-23 | 2013-03-01 | Saint Gobain Technical Fabrics | ELECTROLYTE MATERIAL |
| CN103185781B (en) * | 2011-12-30 | 2015-02-04 | 深圳市亚辉龙生物科技有限公司 | Reagent device for detecting anti-glomerular basement membrane antibody and method thereof |
| CN108409964A (en) * | 2018-05-18 | 2018-08-17 | 东华大学 | Using ionic liquid as poly ion liquid of skeleton and preparation method thereof |
| CN112048277B (en) * | 2020-09-08 | 2023-03-28 | 南方科技大学 | Conductive adhesive and preparation method and application thereof |
| CN114994997B (en) * | 2021-03-01 | 2023-10-13 | 中国科学院上海硅酸盐研究所 | Electrochromic device with mesoporous structure and preparation method thereof |
| CN116515289A (en) * | 2023-05-26 | 2023-08-01 | 金旸（厦门）新材料科技有限公司 | Nylon material for extruded hose and preparation method thereof |
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| US5912093A (en) * | 1997-05-15 | 1999-06-15 | National Science Council | Polyurethane-based polymeric electrolyte and process for producing same |
| US6284412B1 (en) * | 1995-11-15 | 2001-09-04 | Asahi Kasei Kogyo Kabushiki Kaisha | Hybrid polymeric electrolyte and non-aqueous electrochemical device comprising the same |
| US6361709B1 (en) * | 1999-05-26 | 2002-03-26 | Basf Aktiengesellschaft | Optically transparent polymeric solid electrolyte |
| WO2002040578A1 (en) * | 2000-11-17 | 2002-05-23 | Gesimat Gmbh | Ion-conducting polyvinyl acetal film |
| WO2005008326A1 (en) * | 2003-07-16 | 2005-01-27 | Saint-Gobain Glass France | Electrically-controllable film having variable optical and/or energy properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60214833T2 (en) * | 2001-03-07 | 2007-09-06 | Acreo Ab | ELECTROCHROMICAL DEVICE |
| FR2825481B1 (en) * | 2001-05-31 | 2003-07-18 | Commissariat Energie Atomique | FLEXIBLE ELECTROCHROME STRUCTURE AND METHODS OF MAKING THE STRUCTURE |
-
2006
- 2006-12-18 FR FR0655610A patent/FR2910137B1/en not_active Expired - Fee Related
-
2007
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284412B1 (en) * | 1995-11-15 | 2001-09-04 | Asahi Kasei Kogyo Kabushiki Kaisha | Hybrid polymeric electrolyte and non-aqueous electrochemical device comprising the same |
| US5912093A (en) * | 1997-05-15 | 1999-06-15 | National Science Council | Polyurethane-based polymeric electrolyte and process for producing same |
| US6361709B1 (en) * | 1999-05-26 | 2002-03-26 | Basf Aktiengesellschaft | Optically transparent polymeric solid electrolyte |
| WO2002040578A1 (en) * | 2000-11-17 | 2002-05-23 | Gesimat Gmbh | Ion-conducting polyvinyl acetal film |
| WO2005008326A1 (en) * | 2003-07-16 | 2005-01-27 | Saint-Gobain Glass France | Electrically-controllable film having variable optical and/or energy properties |
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| FR2910137B1 (en) | 2009-03-20 |
| FR2910137A1 (en) | 2008-06-20 |
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