WO2000008523A2 - Self-adhesive electrochromic electrode and systems containing same - Google Patents

Self-adhesive electrochromic electrode and systems containing same Download PDF

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Publication number
WO2000008523A2
WO2000008523A2 PCT/EP1999/005244 EP9905244W WO0008523A2 WO 2000008523 A2 WO2000008523 A2 WO 2000008523A2 EP 9905244 W EP9905244 W EP 9905244W WO 0008523 A2 WO0008523 A2 WO 0008523A2
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WO
WIPO (PCT)
Prior art keywords
electrochromic
layer
adhesive
substrate
electrode according
Prior art date
Application number
PCT/EP1999/005244
Other languages
German (de)
French (fr)
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WO2000008523A3 (en
Inventor
Helmut Werner Heuer
Rolf Wehrmann
Jan Weikard
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU53711/99A priority Critical patent/AU5371199A/en
Priority to JP2000564097A priority patent/JP2002522806A/en
Priority to KR1020017001326A priority patent/KR20010053618A/en
Priority to EP99939396A priority patent/EP1103016A2/en
Publication of WO2000008523A2 publication Critical patent/WO2000008523A2/en
Publication of WO2000008523A3 publication Critical patent/WO2000008523A3/en

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Classifications

    • 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
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/44—Arrangements combining different electro-active layers, e.g. electrochromic, liquid crystal or electroluminescent layers

Definitions

  • the present invention relates to an electrochromic electrode which contains an adhesive layer, and to electrochromic arrangements equipped with such an electrode and their use
  • Electrochromic materials change their color through oxidation and reduction processes.
  • the electrochromic material and the ion-storing counterelectrode are connected to one another by an ion-conducting gel electrolyte, so that charge transport can take place between the layers.
  • the optical properties of the electrochromic material change due to redox processes, which can be linked to the exchange of ions, for example protons or metal ions such as lithium ions.
  • the metal ions can thus be released from the structure or stored under the influence of an electric field. The effect can be reversed by changing the polarity of the applied field, as a result of which the electrochromic material returns to its original optical state.
  • the object of the present invention was to develop electrochromic adhesive layers which, instead of the laboriously produced electrochromic metal oxides, should contain organic polymeric electrochromic layers which are easy to apply and which, even under bending stress, do not show any cracking on flexible substrates, as has hitherto been the case with inorganic metal oxide layers .
  • the invention relates to a self-holding electrochromic electrode, comprising an electrically conductive coated substrate made of glass or plastic, which is rigid or flexible and can be designed as a tape or a film, an electrochromic, polymeric, organic material and an adhesive layer.
  • an electrochromic polymer for example poly (3,4-ethylenedioxythiophene
  • the electrochromic electrode preferably contains a removable protective layer on the adhesive layer, which can be continuous or discontinuous.
  • the adhesive layer can be designed as a single or multi-layer construction and exhibits adhesive or adhesive properties under ambient conditions or develops such properties, for example by swelling with solvent or by the influence of elevated temperature or pressure.
  • the adhesive layer preferably contains an ion-storing material.
  • An ion-storing material is a material which has a microstructure which allows ions, preferably protons or metal ions, in particular lithium ions, to be incorporated reversibly, the incorporation or removal being able to be caused by an applied electric field.
  • the adhesive layer can be such that the ion-storing material either exhibits self-adhesive or adhesive properties, or that the ion-storing material is combined with one or more additional materials in the form of separate layers or as a mixture with the ion-storing material, with the result that that the combined construction shows adhesive or adhesive properties.
  • the ion-storing material is arranged between the substrate and the removable protective layer.
  • the electrochromic material and an ion-conducting polymer gel electrolyte are arranged between the substrate and the removable protective layer.
  • the protective layer can each represent a low-energy surface that is easy to pull on without damaging the functional layer underneath.
  • the adhesive layer is preferably a pressure-sensitive layer, ie the layer should adhere when pressed onto a base.
  • electrostatic material refers to an organic polymeric material (preferably polydioxythiophene) that can be reduced or oxidized and can also include embedded ions.
  • the polydioxythiophenes are preferably cationically charged and from structural units of the formula (I)
  • a 1 and A 2 independently of one another are optionally substituted (C j -C ⁇ alkyl or together form optionally substituted (C] -C) alkylene, and
  • Preferred cationic polydioxythiophenes are composed of structural units of the formula (Ia) or (Ib)
  • R j and R 2 independently of one another for hydrogen, optionally substituted (C 1 -C 8 ) -alkyl, preferably (CJ-CJOK in particular (C 1 -C 6 ) -alkyl, (C 2 -C 1 ) -alkenyl, preferably (C2- C 8 ) alkenyl, (C3-C 7 ) cycloalkyl, preferably cyclopentyl, cyclohexyl, (C 7 -C 15 ) aralkyl, preferably phenyl (C 1 -C 4 alkyl), (C6-Cjo) aryl, preferably Phenyl, naphthyl, (-CC 18 ) - alkyloxy, preferably (-C-Cjo) alkyloxy, for example methoxy, ethoxy, n- or iso-propoxy, or (C 2 -C j 8 ) alkyloxy ester and
  • R 3 , R 4 independently of one another for hydrogen - but not simultaneously -, preferably substituted with (C ⁇ -C ⁇ g) alkyl substituted with at least one sulfonate group
  • (CJ-CJO) - in particular (Cj-C 6 ) alkyl, (C 2 -Cj 2 ) alkenyl, preferably (C 2 - C 8 ) alkenyl, (C3-C 7 ) cycloalkyl, preferably cyclopentyl, Cyclohexyl, (C 7 -C 5 ) aralkyl, preferably phenyl (C ) -C 4 ) alkyl, (C 6 -C 10 ) aryl, preferably phenyl, naphthyl, (C 1 -C 18 ) alkyloxy, preferably (C j -C ⁇ 0 ) - alkyloxy, for example methoxy, ethoxy, n- or iso-propoxy or (C 2 -
  • n stands for a number from 2 to 10,000, preferably 5 to 5,000.
  • the electrochromic device structure according to the invention very particularly preferably contains at least one electrically conductive, electrochromic cationic or neutral polydioxythiophene of the formulas (Ia-1) and / or (Ib-1)
  • R 3 has the meaning given above.
  • n represents an integer from 2 to 10,000, preferably 5 to 5,000.
  • polymeric carboxylic acids such as polyacrylic acids, polymethacrylic acids, or polymaleic acids and polymeric sulfonic acids, such as polystyrene sulfonic acids and polyvinyl sulfonic acids, serve as polyanions.
  • polycarbonic and sulfonic acids can also be copolymers of vinylcarbonic and vinylsulfonic acids with other polymerizable monomers, such as acrylic acid esters and styrene.
  • the anion of the polystyrene sulfonic acid is particularly preferred as the counter ion.
  • the molecular weight of the polyacids providing the polyanions is preferably 1,000 to 2,000,000, particularly preferably 2,000 to 500,000.
  • the polyacids or their alkali metal salts are commercially available, for example polystyrene sulfonic acids and polyacrylic acids, or else they can be prepared by known processes (see Houben Weyl, Methods of Organic Chemistry, Vol. E 20 Macromoleculars
  • the polydioxythiophenes carry positive and negative charges in the structural unit.
  • the polydioxythiophenes are obtained by oxidative polymerization. This gives them positive charges, which are not shown in the formulas, since their number and position cannot be determined properly.
  • the electrochromic material can be poly (3,4-ethylenedioxythiophene)
  • PET poly (3,4-ethylenedioxythiophene) polystyrene sulfonate
  • PSS polystyrene sulfonate
  • embedded ions preferably protons or metal ions, in particular lithium ions.
  • Preferred electrochromic electrodes contain as the electrochromic material an electrically conductive polymer, preferably from the substance class of poly (3,4-dioxy thiophenes).
  • Another preferred electrochromic electrode contains ion storage materials, preferably V 2 O 5 , Nb 2 ⁇ 5, Li x V 2 ⁇ 5 , Li 2 Nb 2 O 5 or nickel oxides. In a preferred construction, it has electrochromic or ion storage Material itself does not have an adhesive or adhesive property, but ion-conductive polymer gel electrolytes applied to it.
  • a flexible substrate preferred according to the invention is polyethylene terephthalate (PET) or polyethylene maphthalate (PEN) or flexible glass, each of which is provided with a transparent, electrically conductive coating.
  • the flexible substrate can also be reflective. For example, it can contain a metal layer such as silver as a reflective layer.
  • the transparent, electrically conductive coating can consist of indium tin oxide (ITO), tin dioxide (SnO 2 ) or fluorine-doped tin dioxide (SnO 2 : F), as well as a sufficiently thin metal coating, for example silver.
  • the invention also relates to an electrochromic arrangement which contains the self-adhesive electrochromic electrode according to the invention.
  • a second electrically conductive substrate is brought into contact with the self-adhesive electrode described above.
  • the second electrically conductive system can preferably contain a rigid substrate, for example glass, which is provided with a transparent electrically conductive layer.
  • the second substrate preferably contains an ion storage material, for example V 2 O 5 , Li x V 2 O 5 or a nickel oxide. If the self-adhesive electrode contains the ion storage material, for example V 2 ⁇ 5, Li x V 2 ⁇ 5 or a nickel oxide and a polymeric gel electrolyte, the second substrate preferably contains the electrochromic polymer, for example PEDT / PSS.
  • the invention relates to an electrochromic arrangement which comprises a polymeric electrochromic material, preferably from the sub- punch class of poly- (3,4-ethylenedioxy-thiophenes), and an ion-storing ion storage material, which are separated by an ion-conducting polymer gel electrolyte layer, one substrate made of glass, the second made of flexible plastic or vice versa, and both substrates can be made of plastic.
  • the polymeric, ion-conducting gel electrolyte preferably takes on the function of the adhesive or adhesive layer.
  • the invention relates to a glazing unit that
  • a) contains an electrochromic arrangement which is constructed from an electrochromic layer between two electrically conductive substrates, one of the two substrates being rigid and transparent and the second being flexible and transparent or
  • b) contains an electrochromic arrangement which is constructed from an electrochromic layer between two flexible and transparent electrically conductive substrates and which, as an optionally encapsulated film composite system, can be embedded between rigid or flexible transparent substrates or
  • c) contains an electrochromic arrangement according to a) or b) and additionally contains a further third substrate which has no direct contact with either the first or the second substrate, but is separated by a gas layer or vacuum in order to form a heat transfer barrier.
  • the electrochromic arrangement contains an organic polymeric electrochromic material, preferably from the substance class of the poly
  • the gel electrolyte also preferably takes on the function of the adhesive or adhesive layer.
  • Flexible adhesive tapes, foils, etc., as used in the electrochromic arrangement according to the present invention offer a multitude of advantages over existing systems with regard to the production of complete electrochromic arrangements.
  • the flexible tapes or foils can be delivered in the form of rolls and assembled on site to the desired size, for example by cutting.
  • the present concept offers the possibility of producing large-area arrangements, for example for electrochromic windows in the architectural or automotive sector ("smart windows").
  • FIG. 1A illustrates an electrochromic arrangement 10 which is formed from a rigid and a flexible substrate, which are partially separated from one another. The actual electrochromic functional layers are not shown here.
  • FIG. 1B shows an enlarged cross section through the overall construction of the electrochromic arrangement 10 with all necessary layers.
  • the figure shows a tape or film 12 on a flexible substrate 16 with a transparent electrically conductive layer 18, 20 showing the ion storage material and 22 the ion-conducting gel electrolyte.
  • the flexible substrate 16 is preferably PET, PEN or flexible glass.
  • the transparent electrical conductor 18 is preferably indium tin oxide (ITO), tin dioxide (SnO 2 ), fluorine-doped tin dioxide (SnO 2 : F) or a metal, for example silver.
  • ITO indium tin oxide
  • SnO 2 tin dioxide
  • F fluorine-doped tin dioxide
  • a metal for example silver.
  • the ion storage material 20 is an ion-intercalating material that can store ions, preferably protons or metal ions, in particular lithium ions, and release them again by applying an electrical potential.
  • Suitable ion Storage materials for this purpose consist in vanadium or niobium oxide compounds or in mixtures thereof, or in nickel oxides.
  • VO 5 , Nb Ü5 or nickel oxide is preferably used here.
  • the ion-conducting gel electrolyte 22 use is preferably made of a polymer electrolyte which
  • the electrolyte 22 also serves to adhere the tape or film 12 to the rigid substrate 14. It preferably conducts metal ions back and forth between the ion storage material 20 and the electrochromic polymer material 28, depending on the polarity of the applied electrical voltage. Thin barrier layers, which are not shown in FIG. 1B, can separate the electrolyte 22 from the ion storage material 20 and thereby increase the service life of the electrochromic arrangement. Niobium oxide is an example of a suitable barrier layer.
  • a very particularly preferred base material for the gel electrolyte 22 is the crosslinked polymerization product of lithium ion-conducting monomers, oligomers or polymers. Photocrosslinking when exposed to light is very particularly preferred.
  • the polymer can be swollen with solvent, very particularly preferably propylene carbonate, and the surface can also be wetted with solvent after crosslinking for better adhesion.
  • the electrolyte system can already contain metal ions, very particularly preferably lithium ions, during the crosslinking.
  • the optical properties of the electrochromic material 28 can be determined by applying an electrical voltage to the layers 18 and 26, as well as
  • the most suitable electrochromic material 28 is the poly (3,4-ethylenedioxythiophene) polystyrene sulfonate PEDT / PSS.
  • An aqueous dispersion of this material is available as Baytron P® (Bayer AG, Leverkusen).
  • the tape 30 consists of a flexible substrate 32, which is provided with a transparent electrically conductive layer 34, an ion storage material 36, a thin barrier layer 38 and a polymeric ion-conductive gel electrolyte 40 that adheres or adheres to pressure.
  • the peelable protective layer 42 protects the surface of the adhesive electrolyte layer 40 and is peeled off prior to the lamination of the tape 30 onto a flexible or rigid substrate 44.
  • the substrate 46 can be glass or plastic and can be rigid or flexible.
  • the substrate 44 is provided with an electrically conductive coating 48, which can also be reflective, and with a polymeric electrochromic layer 50.
  • FIG. 2A A second structure of an electrochromic arrangement according to the invention is shown in FIG. 2A.
  • the tape 52 consists of a flexible substrate 54 with an electrically conductive coating 56, the electrochromic polymer material 58 and the pressure-sensitive or adhesive polymeric ion-conductive gel electrolyte layer 60. The latter is protected from injury by the peelable protective layer 62 which occurs prior to lamination the substrate 64 is peeled off.
  • the substrate 64 consists of a flexible or rigid glass or plastic substrate 66, which is provided with an electrically conductive layer 68, which can also be reflective, an ion storage material 70 and a barrier layer 72.
  • the ion storage layer and the electrochromic polymer material can be applied to the respective substrates using known techniques, for example by casting and subsequent annealing or, in the case of the ion storage, also by vapor deposition, sputtering or electrochemically.
  • ion storage layer reference is made to DE-A 19 810 931.
  • electrochromic layer reference is made to DE-A 19 810 932.
  • the polymer electrolyte can be coated on the surface of the tape in the form of light-polymerizable monomers or in the form of prepolymers, the tape then preferably being laminated onto the second substrate and then crosslinked with light.
  • the crosslinking reaction can also take place before the lamination.
  • the electrolyte can also be in the form of an adhesive or adhesive polymer system using known conventional ones
  • the electrochromic arrangement which is manufactured according to the above-mentioned methods, can also be integrated into a glazing unit according to FIG. 3.
  • the glazing unit 80 is distinguished in that it consists of a pair of rigid transparent substrates, for example glass or plastic, 82 and 84, which are kept at a distance from one another by means of the spacer 86.
  • the gap between substrates 82 and 84 defines a thermal barrier that defines the insulation properties of the glazing unit.
  • One of the two substrates is provided with a transparent, electrically conductive layer 88 and is part of the electrochromic arrangement, characterized in that it contains the electrochromic polymer material 90 (for example poly- (3,4-ethylenedioxythiophene) and the ion storage material 94 (for example V 2 ⁇ 5, Nb 2 O 5 or nickel oxide), both through the polymeric gel electrolyte layer
  • the electrochromic polymer material 90 for example poly- (3,4-ethylenedioxythiophene
  • the ion storage material 94 for example V 2 ⁇ 5, Nb 2 O 5 or nickel oxide
  • a substrate 98 which can be flexible and is provided with a transparent, electrically conductive coating 96, is in contact with the ion storage material 94 and completes the complete electrochromic structure.
  • the electrochromic arrangement is connected to a voltage source by means of known contacting measures on the conductive layers 88 and 96.
  • the glazing unit which can also consist of curved substrates 84 and 82, can also be designed such that the substrate 98 is flexible and the gap between the substrates 84 and 82 is so small that there is no cavity. Rather, the substrate 98 can also be in contact with the substrate 82.
  • the glazing unit 80 is produced, for example, by the method described above.
  • the electrochromic polymer 90 is applied to the conductive side 88 of the substrate 84 and the tape, which comprises the substrate 98, the transparent conductive layer 96, the ion storage material 94 and the polymeric gel electrolyte 92, is then laminated onto the electrochromic polymer layer.
  • the polymeric gel electrolyte can also be applied to the electrochromic polymer layer and would therefore not be part of the tape.
  • the electrochromic polymer material can also be part of the band instead of the ion storage material.
  • the self-adhesive electrode according to the invention can be used to build up an electrochromic arrangement in the
  • Glazing in the mobile area for example in the automotive sector with sun roofs, tintable windows in the front, rear and side areas, safety laminated glass systems,
  • Ads for example for advertising material, posters,
  • Example la The solution from Example la) is applied to the conductive side of indium / tin oxide-coated polyethylene terephthalate (ITO-PET) and a uniform layer of the sol is produced using the paint spinner (10 sec
  • the polymer Baytron P (aqueous dispersion of the conductive polymer PEDT / PSS, polyethylenedioxythiophene-polystyrene sulfonate, Bayer AG, Leverkusen) is extracted from the aqueous solution with a spin coater 4 times at 15 seconds at a speed of 1500 rpm onto the electrically conductive Side of an ITO-PET film applied. During the application, the solvent is evaporated using a hair dryer.
  • a transparent, only slightly bluish-colored polymer film is obtained.
  • a measurement of the layer thickness with a profilometer showed a value of 0.6 ⁇ m.
  • the still uncrosslinked gel electrolyte is applied to the ion storage layer from Example 1 with a wet film thickness of 200 ⁇ m and brought into contact with the electrochromic PEDT layer from Example 2: This composite is exposed to UV radiation at a belt speed of 20 m min ( Actual radiator) promotes. This crosslinks the gel electrolyte.
  • a film system is obtained which contains a gel electrolyte which is no longer flowing and which is transparent.
  • the electrochromic cell from Example 2 is in each case at the ITO layers with 2.0 V
  • the electrochromic electrode with PEDT in the layer composite from example 2, together with the ITO-PET substrate, is carefully removed from the hardened gel electrolyte layer. After delamination, the electrode remains with the ion storage layer, which is coated with the gel electrolyte layer.
  • the two electrode sides (ITO-PET / V 2 O 5 / gel electrolyte and PEDT / ITO-PET) are joined together, a slight pressure with a spherical body being sufficient to ensure renewed contact between the gel electrolyte and the PEDT layer to manufacture.
  • the layer composite is contacted and the transmission through the composite is measured (see FIG. 4).

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a self-adhesive electrochromic electrode which contains a substrate having an electrically conductive coating and made of glass or a plastic material, an electrochromic, polymeric organic material and an adhesive layer, as well as to electrochromic systems fitted with such an electrode.

Description

Selbsthaftende elektrochrome Elektrode und diese enthaltende AnordnungenSelf-adhesive electrochromic electrode and arrangements containing it
Die vorliegende Erfindung betrifft eine elektrochrome Elektrode, die eine Haftschicht enthält, sowie mit einer derartigen Elektrode ausgerüstete elektrochrome Anordnungen und deren VerwendungThe present invention relates to an electrochromic electrode which contains an adhesive layer, and to electrochromic arrangements equipped with such an electrode and their use
Elektrochrome Materialien verändern ihre Farbe durch Oxidations- und Reduktionsprozesse. In einer elektrochromen Anordnung wird das elektrochrome Material und die ionenspeichernde Gegenelektrode durch einen ionenleitenden Gel-Elektrolyten miteinander verbunden, so daß Ladungstransport zwichen den Schichten stattfinden kann. Die optischen Eigenschaften des elektrochromen Materials ändern sich durch Redoxprozesse, die mit dem Austausch von Ionen, beispielsweise Protonen oder Metallionen wie Lithiumionen, verknüpft sein können. So können die Metallionen aus dem Ionenspeicher unter dem Einfluß eines elektrischen Feldes aus dem Gefüge freigesetzt oder eingelagert werden. Durch Änderung der Polarität des angelegten Feldes läßt sich der Effekt umkehren, wodurch das elektrochrome Material wieder in seinen ursprünglichen optischen Zustand zurückkehrt.Electrochromic materials change their color through oxidation and reduction processes. In an electrochromic arrangement, the electrochromic material and the ion-storing counterelectrode are connected to one another by an ion-conducting gel electrolyte, so that charge transport can take place between the layers. The optical properties of the electrochromic material change due to redox processes, which can be linked to the exchange of ions, for example protons or metal ions such as lithium ions. The metal ions can thus be released from the structure or stored under the influence of an electric field. The effect can be reversed by changing the polarity of the applied field, as a result of which the electrochromic material returns to its original optical state.
Elektrochrome Haftschichten für elektrochrome Anwendungen auf Basis von anorganischen Metalloxiden, beispielsweise WO3, sind beschrieben in WO 97/40419.Electrochromic adhesive layers for electrochromic applications based on inorganic metal oxides, for example WO 3 , are described in WO 97/40419.
Aufgabe der vorliegenden Erfindung war die Entwicklung von elektrochromen Haftschichten, die anstelle der umständlich herzustellenden elektrochromen Metalloxide leicht aufbringbare organische, polymere elektrochrome Schichten enthalten sollen, die auch bei Biegebeanspruchung auf flexiblen Substraten keine Rißbildung zeigen, wie es bisher bei anorganischen Metalloxid-Schichten der Fall ist.The object of the present invention was to develop electrochromic adhesive layers which, instead of the laboriously produced electrochromic metal oxides, should contain organic polymeric electrochromic layers which are easy to apply and which, even under bending stress, do not show any cracking on flexible substrates, as has hitherto been the case with inorganic metal oxide layers .
Es wurde nun gefunden, daß Haftschichten mit einem elektrochromen Polymer, bei- spielsweise Poly-(3,4-ethylendioxy-thiophen), diese Anforderung erfüllen. Ein Gegenstand der Erfindung ist eine selbsthaltende elektrochrome Elektrode, enthaltend ein elektrisch leitfähig beschichtetes Substrat aus Glas oder aus Kunststoff, das starr oder flexibel ist und als Band oder als Folie ausgeführt sein kann, ein elek- trochromes, polymeres, organisches Material sowie eine Haftschicht.It has now been found that adhesive layers with an electrochromic polymer, for example poly (3,4-ethylenedioxythiophene), meet this requirement. The invention relates to a self-holding electrochromic electrode, comprising an electrically conductive coated substrate made of glass or plastic, which is rigid or flexible and can be designed as a tape or a film, an electrochromic, polymeric, organic material and an adhesive layer.
Die elektrochrome Elektrode enthält vorzugsweise auf der Haftschicht eine abziehbare Schutzschicht, die kontinuierlich oder diskontinuierlich ausgebildet sein kann.The electrochromic electrode preferably contains a removable protective layer on the adhesive layer, which can be continuous or discontinuous.
Die Haftschicht kann als Einfach- oder Mehrfachschicht-Konstruktion ausgeführt sein und zeigt klebende oder haftende Eigenschaften unter Umgebungsbedingungen oder entwickelt solche Eigenschaften, beispielsweise durch Anquellen mit Lösungsmittel oder durch den Einfluß von erhöhter Temperatur oder Druck. Die Haftschicht enthält vorzugsweise ein ionenspeicherndes Material.The adhesive layer can be designed as a single or multi-layer construction and exhibits adhesive or adhesive properties under ambient conditions or develops such properties, for example by swelling with solvent or by the influence of elevated temperature or pressure. The adhesive layer preferably contains an ion-storing material.
Ein ionenspeicherndes Material ist ein Material, das eine MikroStruktur aufweist, die es Ionen, vorzugsweise Protonen oder Metallionen, insbesondere Lithiumionen gestattet, reversibel eingelagert zu werden, wobei die Einlagerung bzw. Auslagerung durch ein angelegtes elektrisches Feld verursacht werden kann.An ion-storing material is a material which has a microstructure which allows ions, preferably protons or metal ions, in particular lithium ions, to be incorporated reversibly, the incorporation or removal being able to be caused by an applied electric field.
Die Haftschicht kann dabei so beschaffen sein, daß das ionenspeichernde Material entweder selber klebende oder haftende Eigenschaften zeigt, oder daß das ionenspeichernde Material mit einem oder mehreren zusätzlichen Materialien in Form von separaten Schichten oder als Mischung mit dem ionenspeichernden Material kombiniert ist, mit dem Resultat, daß die kombinierte Konstruktion haftende oder klebende Eigenschaften zeigt.The adhesive layer can be such that the ion-storing material either exhibits self-adhesive or adhesive properties, or that the ion-storing material is combined with one or more additional materials in the form of separate layers or as a mixture with the ion-storing material, with the result that that the combined construction shows adhesive or adhesive properties.
In einem bevorzugten Aufbau ist das ionenspeichernde Material zwischen dem Substrat und der entfernbaren Schutzschicht angeordnet. In einem anderen bevorzugten Aufbau ist das elektrochrome Material sowie ein ionenleitender polymerer Gel- Elektrolyt zwischen dem Substrat und der entfernbaren Schutzschicht angeordnet.In a preferred construction, the ion-storing material is arranged between the substrate and the removable protective layer. In another preferred construction, the electrochromic material and an ion-conducting polymer gel electrolyte are arranged between the substrate and the removable protective layer.
Die Schutzschicht kann dabei jeweils eine Niedrigenergie-Oberfläche darstellen, die sich leicht bziehen läßt ohne die darunter liegende Funktionsschicht zu verletzen. Die Haftschicht ist bevorzugt eine Druck-sensitive Schicht, d.h. beim Andrücken auf eine Unterlage soll die Schicht haften.The protective layer can each represent a low-energy surface that is easy to pull on without damaging the functional layer underneath. The adhesive layer is preferably a pressure-sensitive layer, ie the layer should adhere when pressed onto a base.
Der Begriff "elektrochromes Material" so wie er hier verwendet wird, bezieht sich auf ein organisches polymeres Material (vorzugsweise Polydioxythiophen), das reduziert oder oxidiert sein kann und auch eingelagerte Ionen beinhalten kann.As used herein, the term "electrochromic material" refers to an organic polymeric material (preferably polydioxythiophene) that can be reduced or oxidized and can also include embedded ions.
Die Polydioxythiophene sind vorzugsweise kationisch geladen und aus Struktureinheiten der Formel (I)The polydioxythiophenes are preferably cationically charged and from structural units of the formula (I)
Figure imgf000005_0001
aufgebaut, in der
Figure imgf000005_0001
built in the
A1 und A2 unabhängig voneinander für gegebenenfalls substituiertes (Cj-C^-Alkyl stehen oder zusammen gegebenenfalls substituiertes (C]-C )-Alkylen bilden, undA 1 and A 2 independently of one another are optionally substituted (C j -C ^ alkyl or together form optionally substituted (C] -C) alkylene, and
für eine ganze Zahl von 2 bis 10.000 vorzugsweise 5 bis 5 000 steht,represents an integer from 2 to 10,000, preferably 5 to 5,000,
und enthalten als Gegenionen vorzugsweise Polyanionen.and preferably contain polyanions as counterions.
Bevorzugte kationische Polydioxythiophene sind aus Struktureinheiten der Formel (Ia) oder (Ib) aufgebaut Preferred cationic polydioxythiophenes are composed of structural units of the formula (Ia) or (Ib)
Figure imgf000006_0001
Figure imgf000006_0001
Figure imgf000006_0002
woπn
Figure imgf000006_0002
woπn
Rj und R2 unabhängig voneinander für Wasserstoff, gegebenenfalls substituiertes (Ci- Cj8)-Alkyl, vorzugsweise (CJ-CJOK insbesondere (Cj-C6)-Alkyl, (C2- Cι2)-Alkenyl, vorzugsweise (C2-C8)-Alkenyl, (C3-C7)-Cycloalkyl, vorzugsweise Cyclopentyl, Cyclohexyl, (C7-C15)-Aralkyl, vorzugsweise Phenyl-(Cι- C^-alkyl, (C6-Cjo)-Aryl, vorzugsweise Phenyl, Naphthyl, (Cι-C18)- Alkyloxy, vorzugsweise (Cι-Cjo)-Alkyloxy, beispielsweise Methoxy, Ethoxy, n- oder iso-Propoxy, oder (C2-Cj 8)-Alkyloxyester steht undR j and R 2 independently of one another for hydrogen, optionally substituted (C 1 -C 8 ) -alkyl, preferably (CJ-CJOK in particular (C 1 -C 6 ) -alkyl, (C 2 -C 1 ) -alkenyl, preferably (C2- C 8 ) alkenyl, (C3-C 7 ) cycloalkyl, preferably cyclopentyl, cyclohexyl, (C 7 -C 15 ) aralkyl, preferably phenyl (C 1 -C 4 alkyl), (C6-Cjo) aryl, preferably Phenyl, naphthyl, (-CC 18 ) - alkyloxy, preferably (-C-Cjo) alkyloxy, for example methoxy, ethoxy, n- or iso-propoxy, or (C 2 -C j 8 ) alkyloxy ester and
R3, R4 unabhängig voneinander für Wasserstoff - jedoch nicht gleichzeitig -, mit mindestens einer Sulfonatgruppe substituiertes (Cι-Cιg)-Alkyl, vorzugsweiseR 3 , R 4 independently of one another for hydrogen - but not simultaneously -, preferably substituted with (Cι-Cιg) alkyl substituted with at least one sulfonate group
(CJ-CJO)-, insbesondere (Cj-C6)-Alkyl, (C2-Cj2)-Alkenyl, vorzugsweise (C2- C8)-Alkenyl, (C3-C7)-Cycloalkyl, vorzugsweise Cyclopentyl, Cyclohexyl, (C7-Cι5)-Aralkyl, vorzugweise Phenyl-(C]-C4)-alkyl, (C6-C10)-Aryl, vorzugsweise Phenyl, Naphthyl, (Cι-C18)-Alkyloxy, Vorzug weise (Cj-Cι0)- Alkyloxy, beispielsweise Methoxy, Ethoxy, n- oder iso-Propoxy oder (C2-(CJ-CJO) -, in particular (Cj-C 6 ) alkyl, (C 2 -Cj 2 ) alkenyl, preferably (C 2 - C 8 ) alkenyl, (C3-C 7 ) cycloalkyl, preferably cyclopentyl, Cyclohexyl, (C 7 -C 5 ) aralkyl, preferably phenyl (C ) -C 4 ) alkyl, (C 6 -C 10 ) aryl, preferably phenyl, naphthyl, (C 1 -C 18 ) alkyloxy, preferably (C j -Cι 0 ) - alkyloxy, for example methoxy, ethoxy, n- or iso-propoxy or (C 2 -
C18)-Alkyloxyester steht.C 18 ) alkyloxy ester.
n für eine Zahl von 2 bis 10.000, vorzugsweise 5 bis 5.000 steht. Ganz besonders bevorzugt enthält der erfindungsgemäße elektrochrome Deviceaufbau mindestens ein elektrisch leitfähiges, elektrochromes kationisches oder neutrales Polydioxythiophen der Formeln (I-a-1) und/oder (I-b-1)n stands for a number from 2 to 10,000, preferably 5 to 5,000. The electrochromic device structure according to the invention very particularly preferably contains at least one electrically conductive, electrochromic cationic or neutral polydioxythiophene of the formulas (Ia-1) and / or (Ib-1)
Figure imgf000007_0001
Figure imgf000007_0001
Figure imgf000007_0002
Figure imgf000007_0002
worinwherein
R3 die obengenannte Bedeutung hat.R 3 has the meaning given above.
n für eine ganze Zahl von 2 bis 10.000, vorzugsweise 5 bis 5.000 steht.n represents an integer from 2 to 10,000, preferably 5 to 5,000.
Als Polyanionen dienen die Anionen von polymeren Carbonsäuren, wie Polyacryl- säuren, Polymethacrylsäuren, oder Polymaleinsäuren und polymeren Sulfonsäuren, wie Polystyrolsulfonsäuren und Polyvinylsulfonsäuren. Diese Polycarbon- und -sulfonsäuren können auch Copolymere von Vinylcarbon- und Vinylsulfonsäuren mit anderen polymerisierbaren Monomeren, wie Acrylsäureestern und Styrol sein.The anions of polymeric carboxylic acids, such as polyacrylic acids, polymethacrylic acids, or polymaleic acids and polymeric sulfonic acids, such as polystyrene sulfonic acids and polyvinyl sulfonic acids, serve as polyanions. These polycarbonic and sulfonic acids can also be copolymers of vinylcarbonic and vinylsulfonic acids with other polymerizable monomers, such as acrylic acid esters and styrene.
Besonders bevorzugt ist das Anion der Polystyrolsulfonsäure als Gegenion. Das Molekulargewicht der die Polyanionen liefernden Polysäuren beträgt vorzugsweise 1.000 bis 2.000.000, besonders bevorzugt 2.000 bis 500.000. Die Polysäuren oder ihre Alkalisalze sind im Handel erhältlich, beispielsweise Polystyrolsulfon- säuren und Polyacrylsäuren, oder aber nach bekannten Verfahren herstellbar (siehe Houben Weyl, Methoden der organischen Chemie, Bd. E 20 MakromolekulareThe anion of the polystyrene sulfonic acid is particularly preferred as the counter ion. The molecular weight of the polyacids providing the polyanions is preferably 1,000 to 2,000,000, particularly preferably 2,000 to 500,000. The polyacids or their alkali metal salts are commercially available, for example polystyrene sulfonic acids and polyacrylic acids, or else they can be prepared by known processes (see Houben Weyl, Methods of Organic Chemistry, Vol. E 20 Macromoleculars
Stoffe, Teil 2, (1987), S. 1141 u.f.).Fabrics, Part 2, (1987), pp. 1141 and others).
Anstelle der für die Bildung der Dispersionen aus Polydioxythiophenen und Polyanionen erforderlichen freien Polysäuren, kann man auch Gemische aus Alkalisalzen der Polysäuren und entsprechenden Mengen an Monosäuren einsetzen.Instead of the free polyacids required for the formation of the dispersions from polydioxythiophenes and polyanions, it is also possible to use mixtures of alkali salts of the polyacids and corresponding amounts of monoacids.
Im Falle der Formel (IM) tragen die Polydioxythiophene positive und negative Ladung in der Struktureinheit. Die Herstellung der Polydioxythiophene ist beispielsweise in EP-A 0 440 957 (=US-A 5 300 575) beschrieben.In the case of the formula (IM), the polydioxythiophenes carry positive and negative charges in the structural unit. The preparation of the polydioxythiophenes is described, for example, in EP-A 0 440 957 (= US-A 5 300 575).
Die Polydioxythiophene werden durch oxidative Polymerisation erhalten. Dadurch erhalten sie positive Ladungen, die in den Formeln nicht dargestellt sind, da ihre Zahl und ihre Position nicht einwandfrei festellbar sind.The polydioxythiophenes are obtained by oxidative polymerization. This gives them positive charges, which are not shown in the formulas, since their number and position cannot be determined properly.
So kann das elektrochrome Material beispielsweise Poly-(3,4-ethylendioxythiophen)For example, the electrochromic material can be poly (3,4-ethylenedioxythiophene)
(PEDT), Poly(3,4-ethylendioxythiophen)polystyrolsulfonat (PEDT/PSS) oder die jeweiligen Formen mit eingelagerten Ionen, vorzugsweise Protonen oder Metallionen, insbesondere Lithiumionen, umfassen.(PEDT), poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDT / PSS) or the respective forms with embedded ions, preferably protons or metal ions, in particular lithium ions.
Bevorzugte elektrochrome Elektroden beinhalten als elektrochromes Material ein elektrisch leitfähiges Polymer, vorzugsweise aus der Substanzklasse der Poly(3,4- dioxy thiophene) .Preferred electrochromic electrodes contain as the electrochromic material an electrically conductive polymer, preferably from the substance class of poly (3,4-dioxy thiophenes).
Eine andere bevorzugte elektrochrome Elektrode beinhaltet Ionenspeicher- materialien, vorzugsweise V2O5, Nb2θ5, LixV2θ5, Li2Nb2O5 oder Nickeloxide. In einer bevorzugten Konstruktion besitzt das elektrochrome oder ionenspeichernde Material selber keine haftende oder klebende Eigenschaft, sondern darauf aufgebrachte ionenleitende polymere Gel-Elektrolyte.Another preferred electrochromic electrode contains ion storage materials, preferably V 2 O 5 , Nb 2 θ5, Li x V 2 θ 5 , Li 2 Nb 2 O 5 or nickel oxides. In a preferred construction, it has electrochromic or ion storage Material itself does not have an adhesive or adhesive property, but ion-conductive polymer gel electrolytes applied to it.
Ein erfindungsgemäß bevorzugte flexibles Substrat stellt das Polyethylenterephthalat (PET) oder Polyethylermaphthalat (PEN) oder flexibles Glas dar, das jeweils mit einer transparenten elektrisch leitfähigen Beschichtung versehen ist. Das flexible Substrat kann dabei auch reflektierend sein. So kann es beispielsweise eine Metallschicht wie Silber als spiegelnde Schicht enthalten. Die transparente elektrisch leitfähige Beschichtung kann aus Indium-Zinn-Oxid (ITO), Zinndioxid (SnO2) oder fluordotiertem Zinndioxid (SnO2:F) sowie aus einem genügend dünnen Metallbelag, beispielsweise Silber, bestehen.A flexible substrate preferred according to the invention is polyethylene terephthalate (PET) or polyethylene maphthalate (PEN) or flexible glass, each of which is provided with a transparent, electrically conductive coating. The flexible substrate can also be reflective. For example, it can contain a metal layer such as silver as a reflective layer. The transparent, electrically conductive coating can consist of indium tin oxide (ITO), tin dioxide (SnO 2 ) or fluorine-doped tin dioxide (SnO 2 : F), as well as a sufficiently thin metal coating, for example silver.
Die Erfindung betrifft auch eine elektrochrome Anordnung, die die erfindungsgemäße selbsthaftende elektrochrome Elektrode enthält. Darin ist ein zweites elektrisch leitfähiges Substrat mit der oben beschriebenen selbsthaftenden Elektrode in Kontakt gebracht.The invention also relates to an electrochromic arrangement which contains the self-adhesive electrochromic electrode according to the invention. A second electrically conductive substrate is brought into contact with the self-adhesive electrode described above.
Bevorzugt kann das zweite elektrisch leitfähige System ein starres Substrat, beispielsweise Glas enthalten, das mit einer transparenten elektrisch leitenden Schicht versehen ist.The second electrically conductive system can preferably contain a rigid substrate, for example glass, which is provided with a transparent electrically conductive layer.
Falls die selbsthaftende Elektrode ein elektrochromes Polymer wie PEDT/PSS und einen ionenleitenden polymeren Gel-Elektrolyten beinhaltet, enthält das zweite Substrat bevorzugt ein Ionenspeicher-Material, beispielsweise V2O5, LixV2O5 oder ein Nickeloxid. Falls die selbsthaftende Elektrode das Ionenspeicher-Material, beispielsweise V2θ5, LixV2θ5 oder ein Nickeloxid und einen polymeren Gel-Elektrolyten beinhaltet, enthält das zweite Substrat bevorzugt das elektrochrome Polymer, beispielsweise PEDT/PSS.If the self-adhesive electrode contains an electrochromic polymer such as PEDT / PSS and an ion-conducting polymeric gel electrolyte, the second substrate preferably contains an ion storage material, for example V 2 O 5 , Li x V 2 O 5 or a nickel oxide. If the self-adhesive electrode contains the ion storage material, for example V 2 θ5, Li x V 2 θ5 or a nickel oxide and a polymeric gel electrolyte, the second substrate preferably contains the electrochromic polymer, for example PEDT / PSS.
In einer bevorzugten Ausfuhrungsform betrifft die Erfindung eine elektrochrome Anordnung, die ein polymeres elektrochromes Material, vorzugsweise aus der Sub- stanzklasse der Poly-(3,4-ethylendioxy-thiophene), und ein ioneneinlagerndes Ionen- speichermaterial beinhaltet, die durch eine ionenleitende polymere Gel-Elektrolytschicht voneinander getrennt sind, wobei ein Substrat aus Glas, das zweite aus flexiblem Kunststoff oder umgekehrt sowie beide Substrate aus Kunststoff sein können. Der polymere, ionenleitende Gel-Elektrolyt übernimmt dabei bevorzugt die Funktion der Haft- oder Klebeschicht.In a preferred embodiment, the invention relates to an electrochromic arrangement which comprises a polymeric electrochromic material, preferably from the sub- punch class of poly- (3,4-ethylenedioxy-thiophenes), and an ion-storing ion storage material, which are separated by an ion-conducting polymer gel electrolyte layer, one substrate made of glass, the second made of flexible plastic or vice versa, and both substrates can be made of plastic. The polymeric, ion-conducting gel electrolyte preferably takes on the function of the adhesive or adhesive layer.
In einer weiteren Ausführungsform betrifft die Erfindung eine Verglasungseinheit, dieIn a further embodiment, the invention relates to a glazing unit that
a) eine elektrochrome Anordnung enthält, die aus einer elektrochromen Schicht zwischen zwei elektrisch leitfähigen Substraten aufgebaut ist, wobei eines von beiden Substraten starr und transparent und das zweite flexibel und transparent ist odera) contains an electrochromic arrangement which is constructed from an electrochromic layer between two electrically conductive substrates, one of the two substrates being rigid and transparent and the second being flexible and transparent or
b) eine elektrochrome Anordnung enthält, die aus einer elektrochromen Schicht zwischen zwei flexiblen und transparenten elektrisch leitfähigen Substraten aufgebaut ist und als gegebenenfalls verkapseltes Folienverbundsystem zwischen starren oder flexiblen transparenten Substraten eingebettet sein kann oderb) contains an electrochromic arrangement which is constructed from an electrochromic layer between two flexible and transparent electrically conductive substrates and which, as an optionally encapsulated film composite system, can be embedded between rigid or flexible transparent substrates or
c) eine elektrochrome Anordnung gemäß a) oder b) enthält und zusätzlich ein weiteres drittes Substrat enthält, das sowohl zum ersten als auch zum zweiten Substrat keinen direkten Kontakt hat, sondern durch eine Gasschicht oder Vakuum getrennt ist, um eine Wärmeübergangsbarriere zu bilden.c) contains an electrochromic arrangement according to a) or b) and additionally contains a further third substrate which has no direct contact with either the first or the second substrate, but is separated by a gas layer or vacuum in order to form a heat transfer barrier.
In allen Fällen a), b) und c) beinhaltet die elektrochrome Anordnung ein organisches polymeres elektrochromes Material vorzugsweise aus der Substanzklasse der Poly-In all cases a), b) and c) the electrochromic arrangement contains an organic polymeric electrochromic material, preferably from the substance class of the poly
(3,4-dioxythiophene), insbesondere der Poly(3,4-ethylendioxythiophene), ein ionen- einlagerndes Ionenspeichermaterial und einen ionenleitenden polymeren Gel-Elektro- lyten, der die ersten beiden Materialien voneinander trennt. Dabei übernimmt der Gel-Elektrolyt bevorzugt auch die Funktion der Haft- oder Klebeschicht.(3,4-dioxythiophenes), in particular poly (3,4-ethylenedioxythiophenes), an ion-storing ion storage material and an ion-conducting polymeric gel electro lyten, which separates the first two materials. The gel electrolyte also preferably takes on the function of the adhesive or adhesive layer.
Flexible Klebebänder, Folien etc. wie sie in der elektrochromen Anordnung gemäß der vorliegenden Erfindung eingesetzt werden, bieten eine Vielzahl von Vorteilen gegenüber bestehenden Systemen in Bezug auf die Fertigung von kompletten elektrochromen Anordnungen. So können die flexiblen Bänder oder Folien in Form von Rollen geliefert und vor Ort auf das gewünschte Maß konfektioniert werden, beispielsweise durch Schneiden. Außerdem bietet das vorliegende Konzept die Möglichkeit der Herstellung von großflächigen Anordnungen, beispielsweise für elektrochrome Fenster im Architektur- oder Automobilbereich ("smart Windows").Flexible adhesive tapes, foils, etc., as used in the electrochromic arrangement according to the present invention, offer a multitude of advantages over existing systems with regard to the production of complete electrochromic arrangements. The flexible tapes or foils can be delivered in the form of rolls and assembled on site to the desired size, for example by cutting. In addition, the present concept offers the possibility of producing large-area arrangements, for example for electrochromic windows in the architectural or automotive sector ("smart windows").
Fig. 1A stellt eine elektrochrome Anordnung 10 dar, die aus einem starren und einem flexiblen Substrat gebildet wird, die teilweise voneinander getrennt sind. Die eigent- liehen elektrochromen Funktionsschichten sind hierbei nicht näher eingezeichnet.FIG. 1A illustrates an electrochromic arrangement 10 which is formed from a rigid and a flexible substrate, which are partially separated from one another. The actual electrochromic functional layers are not shown here.
Fig. 1B stellt einen vergrößerten Querschnitt durch die Gesamtkonstruktion der elektrochromen Anordnung 10 mit allen notwendigen Schichten dar.1B shows an enlarged cross section through the overall construction of the electrochromic arrangement 10 with all necessary layers.
Die Abbildung stellt ein Band oder Folie 12 auf einem flexiblen Substrat 16 mit einer transparenten elektrisch leitfähigen Schicht 18 dar, wobei 20 das Ionenspeichermate- rial und 22 den ionenleitenden Gel-Elektrolyten zeigt. Das flexible Substrat 16 ist dabei bevorzugt PET, PEN oder flexibles Glas. Der transparente elektrische Leiter 18 ist bevorzugt Indium-Zinn-Oxid (ITO), Zinndioxid (SnO2), fluor-dotiertes Zinndioxid (SnO2:F) oder ein Metall, beispielsweise Silber. Flexible Substrate dieserThe figure shows a tape or film 12 on a flexible substrate 16 with a transparent electrically conductive layer 18, 20 showing the ion storage material and 22 the ion-conducting gel electrolyte. The flexible substrate 16 is preferably PET, PEN or flexible glass. The transparent electrical conductor 18 is preferably indium tin oxide (ITO), tin dioxide (SnO 2 ), fluorine-doped tin dioxide (SnO 2 : F) or a metal, for example silver. Flexible substrates of this
Art mit leitfähiger Beschichtung sind bekannt und teilweise kommerziell erhältlich.Kinds with a conductive coating are known and some are commercially available.
Das Ionenspeichermaterial 20 ist ein ionen-interkalierendes Material, das Ionen, vorzugsweise Protonen oder Metallionen, insbesondere Lithiumionen, speichern und durch Anlegen eines elektrischen Potentials wieder freisetzen kann. Geeignete Ionen- speichermaterialien für diesen Zweck bestehen in Vanadium- oder Nioboxid- Verbindungen bzw. in Mischungen daraus, oder in Nickeloxiden.The ion storage material 20 is an ion-intercalating material that can store ions, preferably protons or metal ions, in particular lithium ions, and release them again by applying an electrical potential. Suitable ion Storage materials for this purpose consist in vanadium or niobium oxide compounds or in mixtures thereof, or in nickel oxides.
Bevorzugt eingesetzt wird hierbei V O5, Nb Ü5 oder Nickeloxid. Als ionenleitenden Gel-Elektrolyten 22 verwendet man bevorzugt einen Polymer-Elektrolyten, der dieVO 5 , Nb Ü5 or nickel oxide is preferably used here. As the ion-conducting gel electrolyte 22, use is preferably made of a polymer electrolyte which
Eigenschaft hat, auf Druck haftend oder klebend zu wirken.Has the property of being adhesive or pressure-sensitive.
Der Elektrolyt 22 dient neben dem Ionentransport auch der Haftung des Bandes oder der Folie 12 auf dem starren Substrat 14. Er leitet bevorzugt Metallionen zwischen dem lonenspeichermaterial 20 und dem elektrochromen Polymermaterial 28 hin und her, je nach der Polarität der angelegten elektrischen Spannung. Dünne Barriereschichten die in Fig. 1B nicht dargestellt sind, können den Elektrolyten 22 vom lonenspeichermaterial 20 trennen und dadurch die Lebensdauer der elektrochromen Anordnung erhöhen. Als Beispiel für eine geeignete Barriereschicht kommt Nioboxid in Frage.In addition to the ion transport, the electrolyte 22 also serves to adhere the tape or film 12 to the rigid substrate 14. It preferably conducts metal ions back and forth between the ion storage material 20 and the electrochromic polymer material 28, depending on the polarity of the applied electrical voltage. Thin barrier layers, which are not shown in FIG. 1B, can separate the electrolyte 22 from the ion storage material 20 and thereby increase the service life of the electrochromic arrangement. Niobium oxide is an example of a suitable barrier layer.
Ein ganz besonders bevorzugtes Basis-Material für den Gel-Elektrolyten 22 ist das vernetzte Polymerisationsprodukt von Lithiumionen-leitenden Monomeren, Oligo- meren oder Polymeren. Ganz besonders bevorzugt ist hierbei die Photovernetzung bei Einwirkung von Licht. Das Polymer kann mit Lösungsmittel, ganz besonders bevorzugt Propylencarbonat, angequollen sein, wobei auch nach der Vernetzung eine Benetzung der Oberfläche mit Lösungsmittel zur besseren Haftung erfolgen kann. Das Elektrolytensystem kann bereits bei der Vernetzung Metallionen, ganz besonders bevorzugt Lithiumionen, enthalten. Das starre ober flexible Substrat 14, ganz beson- ders bevorzugt auf Basis von Glas, Polycarbonat oder PET als 24 beinhaltet eine elektrisch leitfähige Schicht 26, sowie das polymere elektrochrome Material 28, besonders bevorzugt Poly-(3,4-ethylendioxythiophen).A very particularly preferred base material for the gel electrolyte 22 is the crosslinked polymerization product of lithium ion-conducting monomers, oligomers or polymers. Photocrosslinking when exposed to light is very particularly preferred. The polymer can be swollen with solvent, very particularly preferably propylene carbonate, and the surface can also be wetted with solvent after crosslinking for better adhesion. The electrolyte system can already contain metal ions, very particularly preferably lithium ions, during the crosslinking. The rigid or flexible substrate 14, very particularly preferably based on glass, polycarbonate or PET as 24, contains an electrically conductive layer 26, and the polymeric electrochromic material 28, particularly preferably poly (3,4-ethylenedioxythiophene).
Die optischen Eigenschaften des elektrochromen Materials 28 lassen sich durch Anlegen einer elektrischen Spannung an die Schichten 18 und 26, sowie durchThe optical properties of the electrochromic material 28 can be determined by applying an electrical voltage to the layers 18 and 26, as well as
Änderung der Polarität verändern. Als elektrochromes Materials 28 kommt ganz besonders bevorzugt das Poly-(3,4- ethylendioxythiophen)-polystyrolsulfonat PEDT/PSS in Frage. Eine wäßrige Dispersion dieses Materials ist als Baytron P® (Fa. Bayer AG, Leverkusen) erhältlich.Change polarity change. The most suitable electrochromic material 28 is the poly (3,4-ethylenedioxythiophene) polystyrene sulfonate PEDT / PSS. An aqueous dispersion of this material is available as Baytron P® (Bayer AG, Leverkusen).
Fig. 2B zeigt schematisch das Herstellungsverfahren einer elektrochromen Anordnung unter Verwendung der erfindungsgemäßen haftenden Bänder oder Folien. Das Band 30 besteht aus einem flexiblen Substrat 32, das mit einer transparenten elektrisch leitfähigen Schicht 34, einem lonenspeichermaterial 36, einer dünnen Barriereschicht 38 und einem auf Druck haftendem oder klebendem polymeren ionenleitenden Gel-Elektrolyten 40 versehen ist. Die abziehbare Schutzschicht 42 schützt die Oberfläche der haftenden Elektrolyt-Schicht 40 und wird vor der Laminierung des Bandes 30 auf ein flexibles oder starres Substrat 44 abgezogen. Das Substrat 46 kann dabei Glas oder Kunststoff darstellen und starr oder flexibel sein. Das Substrat 44 ist mit einer elektrisch leitfähigen Beschichtung 48 versehen, die auch spiegelnd sein kann, sowie mit einer polymeren elektrochromen Schicht 50.2B schematically shows the manufacturing process of an electrochromic arrangement using the adhesive tapes or foils according to the invention. The tape 30 consists of a flexible substrate 32, which is provided with a transparent electrically conductive layer 34, an ion storage material 36, a thin barrier layer 38 and a polymeric ion-conductive gel electrolyte 40 that adheres or adheres to pressure. The peelable protective layer 42 protects the surface of the adhesive electrolyte layer 40 and is peeled off prior to the lamination of the tape 30 onto a flexible or rigid substrate 44. The substrate 46 can be glass or plastic and can be rigid or flexible. The substrate 44 is provided with an electrically conductive coating 48, which can also be reflective, and with a polymeric electrochromic layer 50.
Ein zweiter Aufbau einer erfindungsgemäßen elektrochromen Anordnung ist in Fig. 2A dargestellt. Das Band 52 besteht aus einem flexiblen Substrat 54 mit einer elektrisch leitfähigen Beschichtung 56, dem elektrochromen Polymermaterial 58 und der auf Druck haftenden oder klebenden polymeren ionenleitenden Gel-Elektrolytschicht 60. Letztere wird von der abziehbaren Schutzschicht 62 vor Verletzung geschützt, die vor dem Laminieren auf das Substrat 64 abgezogen wird. Das Substrat 64 besteht aus einem flexiblen oder starren Glas- oder Kunststoffsubstrat 66, das mit einer elektrisch leitfähigen Schicht 68, die auch spiegelnd sein kann, versehen ist, einem lonenspeichermaterial 70 und einer Barriereschicht 72.A second structure of an electrochromic arrangement according to the invention is shown in FIG. 2A. The tape 52 consists of a flexible substrate 54 with an electrically conductive coating 56, the electrochromic polymer material 58 and the pressure-sensitive or adhesive polymeric ion-conductive gel electrolyte layer 60. The latter is protected from injury by the peelable protective layer 62 which occurs prior to lamination the substrate 64 is peeled off. The substrate 64 consists of a flexible or rigid glass or plastic substrate 66, which is provided with an electrically conductive layer 68, which can also be reflective, an ion storage material 70 and a barrier layer 72.
Die Ionenspeicherschicht sowie das elektrochrome Polymermaterial können auf die jeweiligen Substrate mit bekannten Techniken aufgebracht werden, beispielsweise durch Gießen und anschließende Temperung oder im Falle des Ionenspeichers auch durch Aufdampfen, Aufsputtern oder elektrochemisch. Zur Herstellung der Ionen- speicherschicht sei auf DE-A 19 810 931 verwiesen. Zur Herstellung der elektrochromen Schicht sei auf DE-A 19 810 932 verwiesen.The ion storage layer and the electrochromic polymer material can be applied to the respective substrates using known techniques, for example by casting and subsequent annealing or, in the case of the ion storage, also by vapor deposition, sputtering or electrochemically. For the production of the ion storage layer, reference is made to DE-A 19 810 931. For the production of the electrochromic layer, reference is made to DE-A 19 810 932.
Der Polymer-Elektrolyt kann auf die Oberfläche des Bandes in Form von Licht-poly- merisierbaren Monomeren oder in Form von Präpolymeren beschichtet werden, wobei das Band danach auf das zweite Substrat vorzugsweise auflaminiert wird und anschließend die Vernetzung mit Licht erfolgt. Die Vernetzungsreaktion kann jedoch auch vor dem Auflaminieren erfolgen. Man kann den Elektrolyt jedoch auch in Form eines haftenden oder klebenden Polymersystems mittels bekannter konventionellerThe polymer electrolyte can be coated on the surface of the tape in the form of light-polymerizable monomers or in the form of prepolymers, the tape then preferably being laminated onto the second substrate and then crosslinked with light. However, the crosslinking reaction can also take place before the lamination. However, the electrolyte can also be in the form of an adhesive or adhesive polymer system using known conventional ones
Methoden, wie Gießen oder Aufcoatern, beispielsweise Roll-coating, auf die Oberfläche des Bandes aufbringen. Danach kann das Band auf das zweite Substrat auflaminiert werden.Apply methods such as casting or coating, for example roll coating, to the surface of the belt. The tape can then be laminated onto the second substrate.
Die elektrochrome Anordnung, die nach obengenannten Methoden gefertigt wird, kann auch in eine Verglasungseinheit gemäß Fig. 3 integriert werden. Die Verglasungseinheit 80 ist dadurch ausgezeichnet, daß sie aus einem Paar starrer transparenter Substrate, beispielsweise Glas oder Kunststoff, 82 und 84 besteht, die mittels des Distanzhalters 86 zueinander auf Abstand gehalten werden. Die Lücke zwischen den Substraten 82 und 84 definiert eine thermische Barriere, die die Isolationseigenschaften der Verglasungseinheit ausmacht. Eines der beiden Substrate ist mit einer transparenten elektrisch leitfähigen Schicht 88 versehen und ist Teil der elektrochromen Anordnung, dadurch gekennzeichnet, daß es das elektrochrome Polymermaterial 90 (z.B. Poly-(3,4-ethylendioxythiophen) und das lonenspeichermaterial 94 (z.B. V2θ5, Nb2O5 oder Nickeloxid) enthält, die beide durch die polymere Gel-ElektrolytschichtThe electrochromic arrangement, which is manufactured according to the above-mentioned methods, can also be integrated into a glazing unit according to FIG. 3. The glazing unit 80 is distinguished in that it consists of a pair of rigid transparent substrates, for example glass or plastic, 82 and 84, which are kept at a distance from one another by means of the spacer 86. The gap between substrates 82 and 84 defines a thermal barrier that defines the insulation properties of the glazing unit. One of the two substrates is provided with a transparent, electrically conductive layer 88 and is part of the electrochromic arrangement, characterized in that it contains the electrochromic polymer material 90 (for example poly- (3,4-ethylenedioxythiophene) and the ion storage material 94 (for example V 2 θ5, Nb 2 O 5 or nickel oxide), both through the polymeric gel electrolyte layer
92 voneinander getrennt sind. Ein Substrat 98 das flexibel sein kann und mit einer transparenten elektrisch leitfähigen Beschichtung 96 versehen ist, steht in Kontakt zum lonenspeichermaterial 94 und vervollständigt den kompletten elektrochromen Aufbau. In der Verwendung ist die elektrochrome Anordnung mittels bekannter Kontaktiermaßnahmen an den leitfähigen Schichten 88 und 96 mit einer Spannungsquelle verbunden. Die Verglasungseinheit, die auch aus gekrümmten Substraten 84 und 82 bestehen kann, kann auch so ausgeführt sein, daß das Substrat 98 flexibel ist und der Spalt zwischen den Substraten 84 und 82 so gering ist, daß kein Hohlraum entsteht. Viel- mehr kann das Substrat 98 auch in Kontakt mit dem Substrat 82 stehen.92 are separated. A substrate 98, which can be flexible and is provided with a transparent, electrically conductive coating 96, is in contact with the ion storage material 94 and completes the complete electrochromic structure. In use, the electrochromic arrangement is connected to a voltage source by means of known contacting measures on the conductive layers 88 and 96. The glazing unit, which can also consist of curved substrates 84 and 82, can also be designed such that the substrate 98 is flexible and the gap between the substrates 84 and 82 is so small that there is no cavity. Rather, the substrate 98 can also be in contact with the substrate 82.
Die Herstellung der Verglasungseinheit 80 wird beispielsweise nach der oben beschriebenen Methode durchgeführt. Dabei bringt man das elektrochrome Polymer 90 auf die leitfähige Seite 88 des Substrates 84 auf und laminiert dann das Band, das das Substrat 98, die transparente Leitschicht 96, das lonenspeichermaterial 94 und den polymeren Gel-Elektrolyten 92 umfaßt, auf die elektrochrome Polymerschicht auf. Alternativ kann der polymere Gel-Elektrolyt auch auf die elektrochrome Polymerschicht aufgebracht werden und wäre damit nicht Bestandteil des Bandes. In wieder einer anderen Variante, kann das elektrochrome Polymermaterial auch Bestand- teil des Bandes sein anstelle des Ionenspeichermaterials.The glazing unit 80 is produced, for example, by the method described above. The electrochromic polymer 90 is applied to the conductive side 88 of the substrate 84 and the tape, which comprises the substrate 98, the transparent conductive layer 96, the ion storage material 94 and the polymeric gel electrolyte 92, is then laminated onto the electrochromic polymer layer. Alternatively, the polymeric gel electrolyte can also be applied to the electrochromic polymer layer and would therefore not be part of the tape. In yet another variant, the electrochromic polymer material can also be part of the band instead of the ion storage material.
Die erfindungsgemäße selbsthaftende Elektrode kann verwendet werden zum Aufbau einer elektrochromen Anordnung in derThe self-adhesive electrode according to the invention can be used to build up an electrochromic arrangement in the
- Architekturverglasung "smart- Windows", Sonnendächer,- Architectural glazing "smart windows", sun roofs,
Verglasung im mobilen Bereich, beispielsweise im Automobilbereich bei Sonnendächern, abdunkelbaren Scheiben im Front-, Heck- und Seitenbereich, Sicherheitsverbundglassystemen,Glazing in the mobile area, for example in the automotive sector with sun roofs, tintable windows in the front, rear and side areas, safety laminated glass systems,
Anzeigen, beispielsweise für Werbemittel, Plakate,Ads, for example for advertising material, posters,
variabel gestaltbaren Spielfeldbegrenzungslinien in Sporthallen. Die Erfindung wird durch die folgenden Beispiele näher erläutert.variably configurable field boundary lines in sports halls. The invention is illustrated by the following examples.
BeispieleExamples
Beispiel 1example 1
Herstellung einer Ionenspeicherschicht (V2O5)Production of an ion storage layer (V 2 O 5 )
a) Herstellung einer Sol-Lösung zur Erzeugung der Ionenspeicherschichta) Preparation of a sol solution for producing the ion storage layer
2,5 g Ammoniumvanadat NH4 (VO3) werden in 25 g Wasser gelöst und 37,5 g des Ionenaustauschers ®Lewatit S100 (Fa. Bayer AG, Leverkusen, Deutschland) hinzugegeben. Anschließend wird 10 Minuten bei Raumtemperatur gerührt. Unter schnellem Rühren gibt man anschließend nochmals 475 g Wasser hinzu und rührt 10 Minuten nach. Die Mischung wird abfiltriert und die erhaltene Lösung 24 Stunden bei Raumtemperatur zur Alterung stehengelassen. Schließlich wird 0,25 g des Benetzungsmittels Fluortensid® FT 248 (Fa. Bayer AG, Leverkusen) hinzugegeben. Diese Lösung ist gebrauchsfertig.2.5 g of ammonium vanadate NH 4 (VO 3 ) are dissolved in 25 g of water and 37.5 g of the ion exchanger ®Lewatit S100 (Bayer AG, Leverkusen, Germany) are added. The mixture is then stirred at room temperature for 10 minutes. With rapid stirring, another 475 g of water are then added and stirring is continued for 10 minutes. The mixture is filtered off and the solution obtained is left to stand for 24 hours at room temperature for aging. Finally, 0.25 g of the wetting agent Fluortensid® FT 248 (Bayer AG, Leverkusen) is added. This solution is ready to use.
b) Gelprozeßb) gel process
Die Lösung aus Beispiel la) wird auf die leitfähige Seite von Indium- /Zinnoxid-beschichtetem Polyethylenterephthalat (ITO-PET) aufgebracht und mit der Lackschleuder eine gleichmäßige Schicht des Sols erzeugt (10 sec. beiThe solution from Example la) is applied to the conductive side of indium / tin oxide-coated polyethylene terephthalate (ITO-PET) and a uniform layer of the sol is produced using the paint spinner (10 sec
1000 U/min). Anschließend tempert man 24 Stunden bei 60°C. Die Schichtdickenmessung mit dem Profilometer ergab 10 bis 20 nm. Beispiel 21000 rpm). Then you anneal at 60 ° C for 24 hours. The layer thickness measurement with the profilometer showed 10 to 20 nm. Example 2
Bau eines elektrochromen FoliensystemsConstruction of an electrochromic film system
Aufbringen eines elektrochromen Polymers auf ein ITO-PET-Substrat:Applying an electrochromic polymer to an ITO-PET substrate:
Das Polymer Baytron P (wäßrige Dispersion des leitfähigen Polymers PEDT/PSS, Polyethylendioxythiophen-polystyrolsulfonat, Fa. Bayer AG, Leverkusen) wird aus wäßriger Lösung mit einer Lackschleuder 4 mal mit je 15 Sekunden bei einer Umdrehungsgeschwindigkeit von 1500 U/min auf die elektrisch leitfähige Seite einer ITO- PET-Folie aufgebracht. Während des Aufbringens wird mittels eines Föns das Lösemittel abgedampft.The polymer Baytron P (aqueous dispersion of the conductive polymer PEDT / PSS, polyethylenedioxythiophene-polystyrene sulfonate, Bayer AG, Leverkusen) is extracted from the aqueous solution with a spin coater 4 times at 15 seconds at a speed of 1500 rpm onto the electrically conductive Side of an ITO-PET film applied. During the application, the solvent is evaporated using a hair dryer.
Man erhält einen durchsichtigen, nur ganz leicht bläulich gefärbten Polymerfilm. Eine Messung der Schichtdicke mit einem Profilometer ergab einen Wert von 0,6 μm.A transparent, only slightly bluish-colored polymer film is obtained. A measurement of the layer thickness with a profilometer showed a value of 0.6 μm.
Herstellung eines Gel-Elektrolyten:Preparation of a gel electrolyte:
7,7 g des ungesättigten aliphatischen Urethanacrylats Roskydal® UA VP LS 2258 (Fa. Bayer AG) wird zusammen mit 0,1925 g (2,5 Gew.-%) Photoinitiator Darocure7.7 of unsaturated aliphatic urethane acrylate Roskydal UA VP LS ® 2258 g (Fa. Bayer AG), together with 0.1925 g (2.5 wt .-%) photoinitiator Darocure
1173 der Fa. Merck, Darmstadt und 0,3 g (3 Gew.-%) Lithium-Trifluormethansulfo- nat der Fa. Aldrich in 2 g trockenem 1 ,2-Propylencarbonat der Fa. Aldrich vermischt. Diese Abmischung ist gießfähig und kann photochemisch vernetzt werden, wodurch ein nicht mehr fließfähiger Gel-Elektrolyt hergestellt werden kann.1173 from Merck, Darmstadt and 0.3 g (3% by weight) of lithium trifluoromethanesulfonate from Aldrich in 2 g of dry 1,2-propylene carbonate from Aldrich. This mixture is pourable and can be photochemically crosslinked, which means that a gel electrolyte that is no longer flowable can be produced.
Herstellung der Gel-Elektrolyt-Schicht:Production of the gel electrolyte layer:
Der noch unvernetzte Gel-Elektrolyt wird auf die Ionenspeicherschicht aus Beispiel 1 mit einer Naßfilmdicke von 200 μm aufgebracht und mit der elektrochromen PEDT- Schicht aus Beispiel 2 in Kontakt gebracht: Dieser Verbund wird mit einer Bandlaufgeschwindigkeit von 20 m min unter einem UV-Strahlten (IST-Strahler) hinwegbe- fbrdert. Dadurch wird der Gel-Elektrolyt vernetzt. Man erhält ein Folien-System, welches einen nicht mehr fließenden Gel-Elektrolyten enthält und transparent ist.The still uncrosslinked gel electrolyte is applied to the ion storage layer from Example 1 with a wet film thickness of 200 μm and brought into contact with the electrochromic PEDT layer from Example 2: This composite is exposed to UV radiation at a belt speed of 20 m min ( Actual radiator) promotes. This crosslinks the gel electrolyte. A film system is obtained which contains a gel electrolyte which is no longer flowing and which is transparent.
Dieses elektrochrome Foliensystem wird in Beispiel 3 näher untersucht.This electrochromic film system is examined in more detail in Example 3.
Beispiel 3Example 3
Funktionstest am elektrochromen FoliensystemFunction test on the electrochromic film system
Die elektrochrome Zelle aus Beispiel 2 wird jeweils an den ITO-Schichten mit 2,0 VThe electrochromic cell from Example 2 is in each case at the ITO layers with 2.0 V
Gleichspannung kurze Zeit kontaktiert, bevor man dann die Polarität der elektrischen Ansteuerung ändert. Man erreicht dadurch ein zyklenmäßiges Ein- und Entfärben der Zelle. Dabei beobachtet man gleichzeitig die zeitliche Änderung der Transmission durch die Zelle.Contacted DC voltage for a short time before changing the polarity of the electrical control. This results in cyclical staining and decolorization of the cell. At the same time, the change in transmission through the cell is observed over time.
Beispiel 4Example 4
Delaminieren des SchichtverbundesDelamination of the layer composite
Die elektrochrome Elektrode mit PEDT im Schichtverbund aus Beispiel 2 wird samt des ITO-PET-Substrates vorsichtig von der ausgehärteten Gel-Elektrolytschicht abgezogen. Zurück bleibt nach dem Delaminieren die Elektrode mit der Ionenspeicherschicht, die mit der Gel-Elektrolytschicht überzogen ist.The electrochromic electrode with PEDT in the layer composite from example 2, together with the ITO-PET substrate, is carefully removed from the hardened gel electrolyte layer. After delamination, the electrode remains with the ion storage layer, which is coated with the gel electrolyte layer.
Beispiel 5Example 5
Laminieren des SchichtverbundesLaminating the layer composite
Die beiden Elektrodenseiten (ITO-PET/V2O5/Gel-Elektrolyt und PEDT/ITO-PET) werden zusammengefügt, wobei ein leichter Druck mit einem balligen Körper ausreicht, um den erneuten Kontakt zwischen der Gel-Elektrolyt- und der PEDT-Schicht herzustellen. Analog zu Beispiel 3 wird der Schichtverbund kontaktiert und die Transmission durch den Verbund gemessen (siehe Fig. 4). The two electrode sides (ITO-PET / V 2 O 5 / gel electrolyte and PEDT / ITO-PET) are joined together, a slight pressure with a spherical body being sufficient to ensure renewed contact between the gel electrolyte and the PEDT layer to manufacture. Analogously to example 3, the layer composite is contacted and the transmission through the composite is measured (see FIG. 4).

Claims

Patentansprttche Patent claims
1. Selbsthaftende elektrochrome Elektrode, enthaltend ein elektrisch leitfähig beschichtetes Substrat aus Glas oder Kunststoff, ein elektrochromes, polyme- res, organisches Material sowie eine Haftschicht.1. Self-adhesive electrochromic electrode, containing an electrically conductive coated substrate made of glass or plastic, an electrochromic, polymeric, organic material and an adhesive layer.
2. Elektrode gemäß Anspruch 1, dadurch gekennzeichnet, daß das Substrat flexibel ist.2. Electrode according to claim 1, characterized in that the substrate is flexible.
3. Elektrode gemäß Anspruch 1, dadurch gekennzeichnet, daß als flexibles3. Electrode according to claim 1, characterized in that as a flexible
Substrat Polyethylenterephthalat (PET), Polyethylennaphthylat (PEN) oder flexibles Glas enthalten ist, das mit Indium-Zinn-Oxid, Zinndioxid, Fluordotiertem Zinndioxid oder mit einem Metall leitfähig beschichtet ist.Substrate polyethylene terephthalate (PET), polyethylene naphthylate (PEN) or flexible glass is included, which is coated with indium tin oxide, tin dioxide, fluorine-doped tin dioxide or with a metal conductive.
4. Elektrode gemäß Anspruch 1, dadurch gekennzeichnet, daß die Haftschicht aus einem ionenleitenden polymeren Gel-Elektrolyten besteht.4. Electrode according to claim 1, characterized in that the adhesive layer consists of an ion-conducting polymeric gel electrolyte.
5. Elektrode gemäß Anspruch 1, dadurch gekennzeichnet, daß das elektrochrome Material ein elektrisch leitfähiger Polymer ist.5. Electrode according to claim 1, characterized in that the electrochromic material is an electrically conductive polymer.
6. Elektrode gemäß Anspruch 1, dadurch gekennzeichnet, daß das elektrochrome Material Poly(3,4-ethylendioxythiophen) ist.6. Electrode according to claim 1, characterized in that the electrochromic material is poly (3,4-ethylenedioxythiophene).
7. Elektrode gemäß Anspruch 1, dadurch gekennzeichnet, daß auf der Haft- Schicht zusätzlich eine Schutzschicht angebracht ist.7. Electrode according to claim 1, characterized in that a protective layer is additionally attached to the adhesive layer.
8. Elektrode gemäß Anspruch 2, dadurch gekennzeichnet, daß sie in Form eines Bandes oder einer Folie ausgebildet ist. 8. Electrode according to claim 2, characterized in that it is designed in the form of a tape or a film.
9. Elektrochrome Anordnung, enthaltend die Elektrode gemäß Anspruch 1 in Kombination mit einem starren oder flexiblen Substrat, das eine elektrisch leitfahige Beschichtung und eine Ionenspeicherschicht enthält.9. Electrochromic arrangement containing the electrode according to claim 1 in combination with a rigid or flexible substrate which contains an electrically conductive coating and an ion storage layer.
10. Verwendung der Anordnung gemäß Anspruch 9 in der Architekturverglasung.10. Use of the arrangement according to claim 9 in architectural glazing.
11. Verwendung der Anordnung gemäß Anspruch 9 in Fahrzeugscheiben.11. Use of the arrangement according to claim 9 in vehicle windows.
12. Verwendung der Anordnung gemäß Anspruch 9 in Anzeigevorrichtungen. 12. Use of the arrangement according to claim 9 in display devices.
PCT/EP1999/005244 1998-08-01 1999-07-22 Self-adhesive electrochromic electrode and systems containing same WO2000008523A2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008034532A1 (en) * 2006-09-20 2008-03-27 Bayer Materialscience Ag Electrochromic arrangement

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE50107822D1 (en) * 2001-01-24 2005-12-01 Gesimat Gmbh Ges Fuer Intellig Electrochromic laminated glass
SG105534A1 (en) * 2001-03-07 2004-08-27 Bayer Ag Multilayered arrangement for electro-optical devices
DE10155168B4 (en) 2001-11-12 2005-02-10 Webasto Systemkomponenten Gmbh & Co. Kg Method for producing a translucent pane structure for vehicles and translucent pane construction
FR2840078B1 (en) 2002-05-22 2004-08-13 Saint Gobain ELECTRICALLY CONTROLLABLE DEVICE WITH VARIABLE OPTICAL AND / OR ENERGY PROPERTIES
DE10329643B4 (en) * 2003-07-01 2016-08-11 Webasto Ag Method for producing a lid with a glass pane and electrical functional elements
KR101296623B1 (en) * 2006-05-12 2013-08-14 엘지디스플레이 주식회사 Fabricating method of plastic substrate
US10852613B2 (en) 2009-03-31 2020-12-01 View, Inc. Counter electrode material for electrochromic devices
US10156762B2 (en) 2009-03-31 2018-12-18 View, Inc. Counter electrode for electrochromic devices
US9261751B2 (en) 2010-04-30 2016-02-16 View, Inc. Electrochromic devices
US11187954B2 (en) 2009-03-31 2021-11-30 View, Inc. Electrochromic cathode materials
US10591795B2 (en) 2009-03-31 2020-03-17 View, Inc. Counter electrode for electrochromic devices
US8582193B2 (en) 2010-04-30 2013-11-12 View, Inc. Electrochromic devices
US9664974B2 (en) 2009-03-31 2017-05-30 View, Inc. Fabrication of low defectivity electrochromic devices
US10261381B2 (en) 2009-03-31 2019-04-16 View, Inc. Fabrication of low defectivity electrochromic devices
JP5763750B2 (en) * 2010-04-30 2015-08-12 ビュー， インコーポレイテッド Electrochromic device, method for manufacturing electrochromic device, and apparatus for manufacturing electrochromic device
US9759975B2 (en) 2010-04-30 2017-09-12 View, Inc. Electrochromic devices
WO2011137104A1 (en) * 2010-04-30 2011-11-03 Soladigm, Inc. Electrochromic devices
US11891327B2 (en) 2014-05-02 2024-02-06 View, Inc. Fabrication of low defectivity electrochromic devices
EP3189373B1 (en) 2014-09-05 2019-11-06 View, Inc. Electrochromic stack with particular counter electrode and method for fabricating such stack
EP4220291A3 (en) 2014-11-26 2023-10-04 View, Inc. Counter electrode for electrochromic devices
CN108962033B (en) * 2018-07-27 2021-05-14 上海天马微电子有限公司 Display module and display device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5138013A (en) * 1990-12-17 1992-08-11 Ford Motor Company Epoxy curable ion-conducting electrolyte useful in electrochromic devices
EP0499115A1 (en) * 1991-02-09 1992-08-19 Dornier Gmbh Solid polymer electrolyte
WO1996013754A1 (en) * 1994-10-26 1996-05-09 Donnelly Corporation Electrochromic devices and methods of preparation
WO1997035351A1 (en) * 1996-03-21 1997-09-25 Showa Denko K.K. Ion conductive laminate and production method and use thereof
WO1997040419A1 (en) * 1996-04-24 1997-10-30 Minnesota Mining And Manufacturing Company Tape for use in manufacturing electrochromic devices
EP0942061A1 (en) * 1998-03-13 1999-09-15 Bayer Ag Electrochromic device based on poly (3,4-dioxythiophene) derivatives

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5138013A (en) * 1990-12-17 1992-08-11 Ford Motor Company Epoxy curable ion-conducting electrolyte useful in electrochromic devices
EP0499115A1 (en) * 1991-02-09 1992-08-19 Dornier Gmbh Solid polymer electrolyte
WO1996013754A1 (en) * 1994-10-26 1996-05-09 Donnelly Corporation Electrochromic devices and methods of preparation
WO1997035351A1 (en) * 1996-03-21 1997-09-25 Showa Denko K.K. Ion conductive laminate and production method and use thereof
WO1997040419A1 (en) * 1996-04-24 1997-10-30 Minnesota Mining And Manufacturing Company Tape for use in manufacturing electrochromic devices
EP0942061A1 (en) * 1998-03-13 1999-09-15 Bayer Ag Electrochromic device based on poly (3,4-dioxythiophene) derivatives

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GUSTAFSSON J C ET AL: "IN SITU SPECTROSCOPIC INVESTIGATIONS OF ELECTROCHROMISM AND ION TRANSPORT IN A POLY(3,4-ETHYLENEDIOXYTHIOPHENE) ELECTRODE IN A SOLID STATE ELECTROCHEMICAL CELL" SOLID STATE IONICS,NL,NORTH HOLLAND PUB. COMPANY. AMSTERDAM, Bd. 69, Nr. 2, 1. Juli 1994 (1994-07-01), Seiten 145-152, XP000574078 ISSN: 0167-2738 *
KYOUNG-HEE LEE ET AL: "ION CONDUCTIVITY STUDIES OF BLENDS OF POLY(METHYL METHACRYLATE)-G-POLY(ETHYLENE GLYCOL) AND POLY(ETHYLENE GLYCOL) COMPLEXED WITH LICF3SO3" JOURNAL OF POLYMER SCIENCE, POLYMER PHYSICS EDITION,US,JOHN WILEY AND SONS. NEW YORK, Bd. 34, Nr. 8, 1. Juni 1996 (1996-06-01), Seiten 1427-1433, XP000592959 ISSN: 0887-6266 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008034532A1 (en) * 2006-09-20 2008-03-27 Bayer Materialscience Ag Electrochromic arrangement
US7518778B2 (en) 2006-09-20 2009-04-14 Bayer Materialscience Ag Electrochromic arrangement

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TW490391B (en) 2002-06-11
DE19834834A1 (en) 2000-02-03

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