• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    STABLE ELECTRONOMIC MODULE. The present invention relates to an electrochromic module comprising a first substrate and a second substrate, where the first and / or the second substrate are / are electrically conductive or are / are respectively equipped with an electrically conductive coating, a coating composed of a electrochromic polymer arranged on the substrate or conductive coating, an ion storage layer arranged on the substrate or conductive coating, and an electrolyte arranged in series electrical connection between the electrochromic coating and the ion storage layer. The electrochromic polymer is a substantially linear condensation polymer composed of a tetraarylbenzidine and an aromatic (hetero) diol, which can be reversibly switched between more than two redox states in a voltage-controlled manner, where the condensation polymer is colorless in one redox state and colored in at least two redox states. The electrolyte is a polymer gel electrolyte. With only one electrochromic material, it is possible to represent more than two color states and at the same time obtain a large number of switching cycles without an appreciable decrease in electrochromic properties, a high electrochromic contrast and a high electrochromic efficiency of the modules (... ).
    公开号:BR112013022298B1
    申请号:R112013022298-0
    申请日:2012-03-02
    公开日:2021-03-16
    发明作者:Gulnara Konkin；Mario Schrodner；Hannes Schache；Dietrich Raabe
    申请人:Thüringisches Institut für Textil - und Kunststoff-Forschung e.V.；
    IPC主号:
    专利说明:

    [0001] The present invention relates to an electrochromic module comprising a first substrate, a second substrate, the first and / or the second substrate being electrically conductive or having been provided, respectively, with an electrically conductive first coating or with a second electrically conductive coating, a coating of an electrochromic polymer disposed on the first substrate or the first conductive coating, an ion storage layer disposed on the second substrate or the second conductive coating and an electrically connected electrolyte in series disposed between the electrochromic coating and the ion storage layer.
    [0002] It is a feature of the inventive electrochromic module that it can be reversibly switched under voltage control between more than two color states and has, after a large number of switching cycles without any significant decline in electrochromic properties, a high electrochromic contrast and high electrochromic efficiency with fast switching kinetics, and is additionally leak-proof.
    [0003] The electrochromic polymer used is an essentially linear condensation polymer formed from a substituted tetrafenylbenzidine and a (hetero) arylenebis-phenylmethanol of the generic structural formula (I), (II), (III) or (IV )

    [0004] where R1 and R2 are identical or different and are each an alkoxy group, a halogen atom, a cyano group or a hydrocarbyl radical having 1-10 carbon atoms, preferably an alkyl group, an allyl group, or a vinyl group, and R3 is a divalent radical of an optionally substituted heteroaromatic or aromatic compound, preferably benzene, a dialkyl hydroquinone ether, diphenyl ether, biphenyl or naphthalene.
    [0005] Electrochromic modules for use as light filters, displays, glare-free rear view mirrors and the like are known. These involve oxidation and reversible electrochemical reduction of active redox materials such as tungsten oxides, viologene or various polymers such as polyethylene, polyethylene dioxythiophene (PEDOT), polyaniline inter alia, which change their color. Although the various known electrochromic systems work well in individual cases, there are also a number of disadvantages. Electrochromic materials such as bipyridinium compounds (viologens) can be switched between three redox forms, reversibly from dation to the radical cation and irreversibly to the uncharged form. In this case, the pimerization of the radical cations (formation of a π complex through electron planes π) causes an altered absorption spectrum and has an adverse effect on the color contrast and life span of EC systems.
    [0006] Stabilizing materials are required, such as metallocenes and metallocene derivatives (DE 102007037619A1, US 2009 / 0259042A1, DE 102008024260B4) and also other known compounds, for example, from EP 1288275A2 and DE 102006061987, which, by guaranteeing a reversible anodic component reaction, it ensures an improved life of the electrochromic switching formulation - cathode (preferably 4,4'-bipyridinium salts) with respect to long-term contrast stability. Here, however, there are problems with color contrast and lifespan in the same way. In long-term studies, formation of metallocenium cations becomes noticeable through the formation of a yellow-brown layer on the anode. In addition, the addition of metallocenes to an electrochromically active formulation leads to separation processes that have been uncontrolled until today, for example, the deposition of ferrocene aggregates.
    [0007] Most electrochromic materials of significance for applications are switchable only between two colors: viologenes (in-color θ blue / violet), tungsten oxide (WO3) (light blue θ blue), poly-3-hexylthiophene (violet θ blue), polyethylenedioxythiophene (PEDOT-PSS) (light blue θ dark blue). Thus it is possible to implement only two-color filters or only monochrome displays.
    [0008] In addition, many electrochromic materials, for example WO3 or PEDOT_PSS, are merely pseudo-colorless in thin layers, and so they are only of limited suitability for applications where the colorless state is required over a wide range of lengths wave (500-1000 nm).
    [0009] Numerous studies have been conducted so far on organic materials using the electrochromic effect. The great advantage of electrochromic polymers and their controllable multicromicity through modification of the chemical structure, and the inexpensive production of arbitrarily thin large-area layers on glass or metal substrates and on flexible films and textiles.
    [00010] Known polymers suitable for electrochromic applications are polythiophenes, polypyrrole, polyphenylenovinylenes and polyaniline. However, these electrochromic conductive polymers have a tendency to change under air, especially with regard to electrical properties and their electrochemical stability, and as a result they have only a short life. That is why it is important to encapsulate the EC modules and protect them from external influences. In this context, the necessary rigid encapsulation impairs flexibility. In addition, such polymers have a low glass transition temperature, and polypyrrole and polyanyl, for example, have poor solubility, and thus are only processable with difficulties. These disadvantages are serious impediments to their practical use.
    [00011] Particular polymers having di- or tri-arylamine units are known as drilling conductors, electroluminescent materials and light-emitting materials, as well as multi-colored electrochromes (W. Holzer et al., Optical Materials 15, 2000 , 225-235).
    [00012] Examples of the use of diphenylamine and its derivatives as an electrochromic material or in combination with anthraquinones are described in US 4752119. It has been proposed that a solution of a diphenylamine and conductive salt in a chemically stable organic solvent (preferably propylene carbonate) between two electrodes is used. A layer of TiO2 dispersion was applied to an electrode, in order to better understand the color change over the white background. As a result of applying a voltage of 1.0 V to 1.5 V, the solution takes on a green color. If the voltage is increased to 2.2 V, a blue-green color is formed in the solution. If the voltage is switched off, the system returns to the colorless ground state via diffusion. After 106 switching cycles, only relatively small electrochromic deteriorations in the cell were recorded. However, such systems comprising liquid media are problematic in terms of operating temperatures and life span; therefore, they have to be hermetically encapsulated.
    [00013] The invention according to DE 3717917 relates to a new polymer consisting of repeating units of N, N, N ', N'-tetrafenyl-p-phenylene diamine and has electrochromic properties. The polymer is soluble in organic solvents and only becomes insoluble once it has been doped with an electron receptor and then de-doped. This polymer film shows a yellow color in the 0.3 V potential region (with respect to Ag / AgCl), a green color in the oxidized state of the first stage at 0.85 V, and a dark blue color in the oxidized state of second stage at 1.2 V. An electrochromic dial was produced using the following steps: a transparent glass plate was subjected to the vapor deposition of an MgF2 insulation film (80 nm) outside the dial region, then reversed - taken with the aforementioned polymer from a chloroform solution (200 nm), subsequently doped with iodine at 100oC and then de-doped under high vacuum. On another glass plate coated with a layer of graphite fiber, a film of Prussian blue (300 nm) was deposited electrolytically. Between the two sheets of glass, a porous bottom panel made of alumina was placed, and the two electrodes were sealed. The electrolyte used was a 1 mol / L solution of Li-ClO4 in propylene carbonate. This electrochromic display has been switched repeatedly up to 105 times by applying a coloring voltage of 8 V and an illumination voltage of -8 V. In the course of this, only a small change in the amount of charge was determined in the oxidation reaction compared to starting value. The production of the electrochromic dial is a multi-stage operation, combined with several different technological operations (doping with iodine at 100oC, doping under high vacuum, electrolytic deposition of Prussian blue), which lead to increased technical and technical complexity. investment. In addition, the coloring and lighting voltages of +/- 8 V are very high compared to conventional EC cells and are economically disadvantageous.
    [00014] DE 3615379 A1 describes a glare-free mirror. The first electrochromic layer is formed from a conjugated polymer such as a substituted or unsubstituted triphenylamine, and the other EC layer is a transition metal oxide, such as WO3. In the described process, a film is applied to the electrode from appropriate triphenylamine monomer or polymer solutions using a coating process and is subsequently polymerized or cross-linked using oxidizing agents, such as iodine, antimony pentafluoride, arsenic pentafluoride, or iron oxide. Still a film-forming medium is an electrolytic polymerization from a monomer solution. For example, such a mirror consists of 4,4'-dichlorotriphenylamine polymer and layers of WO3 EC with an electrolyte solution of LiClO4 in propylene carbonate with 3% by weight of water. The reflection of the mirror in the ground state is about 70%. In the case of applying a voltage of about 1.45 V, the mirror will turn dark blue within about 4 s, and thus the reflection is reduced to about 10%. A voltage of about -0.35 V led to discoloration of the mirror. Subsequent staining (1.1 V, 15 s) and discoloration (-0.4 V, 90 s) were stably reproducible even after 30,000 repetitions. In situ polymerization or crosslinking of the coating film has the disadvantage that residues of the oxidizing agent in the film can lead to unwanted side reactions in the event of repeated oxidation and reduction, and as a result of an unsatisfactory life of the device. Likewise, it yields an additional methodological step for practical use.
    [00015] Electron-rich triphenylamines have a tendency to be oxidized in the presence of oxygen and light to form an unstable radical cation, which still dimerizes to a tetrafenylbenzidine. This oxidation leads to both, the yellowing of the polymer layers and a limitation in the duration of the EC elements. By changing a group in the para-phenyl position, the dimerization reaction can be significantly reduced. However, it has recently been published that the conjugated poly- (4-methoxytriphenylamine) homopolymer has only a moderately stable EC effect up to about 50 cycles (G.-S. Liou et al., Journal of Polymer Science: Part A: Polymer Chemistry, (2007), V. 45, 3292-3302).
    [00016] Preparation and basic electrochemical properties of polymers having aryl-substituted arylenediamine are present in DE 19832943. It has been found that the electrooxidation of a solution of a 3.3 'substituted triphenyldiamine dimer polymer (TPD polymer) originates reversibly a blue color .
    [00017] It is desirable to use TPD polymers and tetraarylbenzidines as electrochromic materials in an electrochromic module with an appropriate electrolyte and an appropriate ion storage layer, which ensures the performance of redox reactions with favorable cyclic periodicity and, therefore, a stable EC effect.
    [00018] It is an objective of the invention to provide an electrochromic module that is perfectly colorless within a wide wavelength range (500-1100 nm) and, in contrast to the prior art, can be produced in a few technologically simple, environmentally friendly steps and cockroaches. In addition, it is an objective of the invention to show more than two color states with only one electrochromic material and, at the same time, to obtain a large number of switching cycles without any significant decline in electrochromic properties, a high electrochromic contrast and a high electro- chromic efficiency of the modules with effective switching kinetics.
    [00019] The objective is obtained through an electrochromic module comprising a first substrate, a second substrate, the first and / or second substrate being electrically conductive or having been provided, respectively, with an electrically conductive first coating or with a second electrically coating conductive, a coating of an electrochromic polymer disposed on the first substrate or the first conductive coating, an ion storage layer disposed on the second substrate or the second conductive coating and an electrically connected electrolyte in series disposed between the electrochromic coating and the layer ion storage, characterized by the fact that the electrochromic polymer is an essentially linear condensation polymer that was formed from a tetraarylbenzidine and an aromatic (hetero) diol and can be reversibly switched under voltage control between more than two redox states , the condensation polymer being colorless in a redox state and colored in at least two redox states, and where the electrolyte (7) is a polymeric gel electrolyte.
    [00020] In the context of the present invention, the first substrate, which is optionally equipped with a first conductive coating, and the electrochromic coating disposed on the first substrate or on the first conductive coating are also referred to collectively as the working electrode. Similarly, the second substrate, which is optionally equipped with a second conductive coating, and the ion storage layer disposed on the second substrate or on the second conductive coating are also referred to collectively as the counter electrode.
    [00021] The invention proceeds from the known structure of electrochromic modules, and the electrochromic properties of the inventive polymers in combination with a polymeric gel electrolyte and an ion storage layer are described.
    [00022] The polymer, which is redox-stable according to the invention, is a condensation polymer of tetraarylbenzidine-diol, preferably a copolymer of the following generic structural formula I, II, III or IV:

    [00023] where R1 and R2 are identical or different and are each an alkoxy group, a halogen atom, a cyano group or a hydrocarbyl radical having 1-10 carbon atoms, preferably an alkyl group, an allyl group, or a vinyl group, and R3 is several aromatic radicals. R3 therein is a derivative of aromatic or hetero-romantic compounds, preferably benzene, dialkyl ethers of hydroquinone, diphenyl ether, biphenyl, naphthalene and other aromatic and heteroaromatics, and their compounds.
    [00024] These polymer films are perfectly colorless and (in the region of visible light) transparent in the uncharged state and can be colored and discolored using a relatively low voltage.
    [00025] The fact that the polymers used in this patent application (in a redox state) are colorless is a major advantage over known EC polymers (polythiophenes, polypyrroles, polyphenylenovinylenes, polyaniline and PEDOT-PSS), which are colored in both states , oxidized and reduced. For many applications in which device transparency is required / desired outside of colored states (including dials, windows, glasses), they are therefore perfectly suited.
    [00026] The inventive polymers essentially have a linear structure and a high glass transition temperature (Tg> 200oC). It is advantageous that the polymers are stable under air in the form of thin films and do not require any inert conditions in the processing course. In addition, they have good solubility in solvents such as dioxane, chloroform, dichloromethane, chlorobenzene and toluene, as a result of which it is possible to produce arbitrarily thin layers from solutions on glass or metal substrates, or also on flexible films and textiles , by means of spinning coaters, doctor blade technology, roll-to-roll and printing processes, and spreading processes, the layer thicknesses are between 50 nm and 1μm, preferably 200 to 500 nm. In contrast to the prior art, the inventive polymer layers do not require any post-treatment (crosslinking, polymerization, doping, de-doping), as a result of which the technological procedure is significantly simplified. At the same time, however, they are insoluble in water, alcohols, aliphatic hydrocarbons, propylene carbonate, ionic liquids, for example, ethylmethylimidazolium bis (trifluoromethylsulfonyl) imide (EMITf2N) and in 1-ethyl-3-methylimidazolium tetrafluoroborate, which be used as electrolyte in electrochromic modules.
    [00027] According to the invention, EC polymers form homogeneous thin layers (approximately 200-500 nm) from solutions having a polymer content of 0.5 to 30 weight percent, preferably 1 to 3 weight percent , on different flexible and glass substrates, which obtain an efficiency in the EC module of up to 950 cm2 / C and an optical contrast of up to 55% for the blue color.
    [00028] The inventive polymers are oxidized in an electrochromic module in combination with a polymeric gel electrolyte (for example, based on EMITf2N) and an ion storage layer with a voltage of about 0.4 V applied to the electrode as a result that the module takes on a homogeneous orange color. In addition, the further oxidation of the EC polymer with the application of a voltage of 0.9 V to the EC module results in a homogeneous blue color. In this case, the orange color state is exceeded. When the voltage drops to -1.0 V, the EC module returns to the colorless state. More particularly, the invention provides EC modules comprising the polymers mentioned above, which can be switched when desired between colorless - clear and colored (for example, colorless / oranges and / or colorless / blue) and between two colors (for example, orange / blue), or also between three states (colorless / orange / blue).
    [00029] Due to the excellent combination of EC polymers used, polymeric electrolyte gel and ion storage layer, the inventive electrochromic modules exhibit very good switching kinetics from blue to colorless in 2 seconds (88% optical contrast) and from colorless to blue in 7 seconds (90% optical contrast, area 3.5 cm2).
    [00030] In addition, EC polymers, with a voltage application of about 0.4 V, have a wide maximum absorption of long wave (À = 1300 nm) with an optical contrast of about 14%.
    [00031] Inventive EC modules comprising EC polymers in combination with an EMITf2N-based polymeric gel electrolyte and an ion storage layer exhibit a stable EC effect above at least 10,000 and preferably at least 20,000 colorless / blue switching cycles .
    [00032] In the invention, a polymer-based or gel-type electrolyte comprising a dissolved lithium salt is used. Gel-forming polymers are, for example, poly (vinylidene-co-hexafluoropropylene) fluoride (PVDF-HFP), polyacrylonitrile (PAN) or polyl (methyl methacrylate) (PMMA). Preferred solvents are ionic liquids such as 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (EMITf2N). Other non-exclusive examples of solvents are propylene carbonate, mixtures of propylene carbonate / ethyl carbonate / diethyl carbonate and other carbonates. In addition, the polymer-based electrolyte contains, in a concentration of 0.1 mol / L to 1 mol / L, a lithium salt such as LiTf2N, LiTfO (lithium trifluoromethanesulfonate) or LiClO4 (lithium perchlorate). The conductive salt and gel-forming polymer are entirely dissolved in the electrolyte and thus do not cause any electrolyte staining. As well as high conductivity (up to 6 mS / cm (EMITf2N, LiTf2N, PVDF-HFP)), the gel electrolyte particularly has good optical transparency in the visual range.
    [00033] In a preferred embodiment of the invention, the counter electrode comprises an ion storage layer that to an extent of more than 50% by weight, preferably more than 60% by weight, of a material selected from the group consisting of in tungsten oxide, nickel oxide, cerium oxide, titanium oxide, molybdenum oxide, vanadium oxide (WO3, NiO, CeO2, TiO2, MoO3, V2O5) and their mixtures. Ion storage layers based on mixed oxides of CeO2-TiO2, which are based on the principle of insertion of Li + into CeO2, are particularly preferred. Its main task is to quickly and entirely compensate for the charge diverted to the working electrode. A conventional CeO2-TiO2 mixed oxide electrode having a charge storage density of up to 26 mC / cm2 using a sol-gel process was used, this having already been described in the literature [C.O. Avellane-da et al., Thin Solid Films 471, (2005) 100-104, A. Verma et al., Thin Solid Films 516, (2008) 4925-4933].
    [00034] The invention is illustrated in detail below by figures. The figures show:
    [00035] Figures 1-2 each an electrochromic module with multilayer structure;
    [00036] Fig. 3 the electrical circuit diagram of an electrochromic module;
    [00037] Fig. 4 a cyclic voltamogram of an electrochromic module;
    [00038] Fig. 5 the spectral transmission of an electrochromic module in three different switching states;
    [00039] Figs. 6-7 the graphic of electrical current upset in an electrochromic module during switching operations; and
    [00040] Fig. 8 the time-dependent transmission during a switching operation.
    [00041] Fig. 1 shows an inventive electrochromic module 10 with a first substrate 1 and a second substrate 4. The first substrate 1 and the second substrate 4 can each consist of a transparent material, such as float glass, quartz glass, a polymer film, a metal sheet, or a transparent, semi-transparent or non-transparent textile. The second substrate 4 can also consist of a non-transparent, ceramic, metallic or textile polymeric material. Preferably, the first and / or second substrate 1,4 are each provided with a conductive coating, 2 and 5 respectively, formed from the same or different materials. Conductive coatings 2 and 5 consist, for example, of a transparent conductive oxide (TCO) such as tin oxide or zinc oxide, aluminum doped tin oxide (ZAO), indium tin oxide (ITO) or tin oxide doped with fluorine (FTO), a metal, for example gold, platinum or stainless steel, or a conductive polymer, for example, poly-3,4-ethylenedioxythiophene poly (styrenesulfonate) (PEDOT-PSS). In alternative embodiments of the invention, the first substrate 1 and / or the second substrate 4 consists of an intrinsically conductive textile comprising metallic or metallized filaments. In the case of using a substrate 1 and / or 4 made of an intrinsically conductive textile, there is no conductive coating 2 or 5.
    [00042] On the substrate 1 optionally equipped with the conductive coating 2 there is arranged a coating 3 consisting of the electrochromic polymer described above, that is, of an essentially linear condensation polymer formed from a tetraarylbenzidine and an aromatic (hetero) diol. The coating 3 is produced by applying an electrochromic polymer solution using known processes, such as spreading, doctor blade coating or spinning coating, for substrate 1 or for conductive coating 2. On substrate 4 optionally equipped with the conductive coating 5 an ion storage layer 6 consisting of more than 50% by weight, preferably more than 80% by weight, of a material selected from the group comprising cerium oxide, titanium oxide, oxide is arranged tungsten, nickel oxide, molybdenum oxide, vanadium oxide (CeO2, TiO2, WO3, NiO, MoO3, V2O5) and mixtures thereof, and more preferably from mixed CeO2-TiO2 oxide. The ion storage layer 6 is preferably produced by applying a dispersion of one of the mentioned oxides and subsequently drying and optionally sintering. Alternatively, the ion storage layer 6 is produced by deposition from the vapor phase, for example, by means of CVD or PVD.
    [00043] The electrochromic module 10 further comprises a polymeric gel electrolyte 7 which is disposed between the electrochromic coating 3 and the ion storage layer 6 and comprises at least one cross-linked polymer such as PVDF-HFP, PAN or PMMA, at least one liquid ionic as 1-ethyl-3-methyl imidazolium bis- (trifluoromethylsulfonyl) imide, propylene carbonate, mixtures of propylene carbonate / ethylene carbonate / diethyl carbonate and at least one lithium salt such as LiTf2N, LiTfO or LiClO4.
    [00044] According to the invention, the polymeric gel electrolyte 7 is disposed between the electrochromic coating 3 and the ion storage layer 6 so that the electrochromic coating 3, the polymeric gel electrolyte 7 and the storage layer of ions 6 are electrically connected in series (see fig. 3). In the same way, electrochromic modules are also envisaged in which substrate 1 and / or substrate 4 consists of an intrinsically electrically conductive textile material, or one that has been equipped with a conductive coating 2 and / or 5, the gel electrolyte polymeric 7 penetrating and filling the pores of substrate 1 and / or 4 and enclosing its conductive filaments.
    [00045] Optionally, the electrochromic module 10 is equipped on the edge side with a seal 8. Seal 8 consists, for example, of a polymeric material and surrounds the edge of the polymeric gel electrolyte layer 7. The seal preferably extends partially or entirely on the edges of substrates 1 and 4.
    [00046] Fig. 2 further shows an electrochromic module 20 according to the present invention. Module 20 comprises a structured conductive coating 2A and / or a structured conductive coating 5A. In appropriate configurations, in addition, a structured electrochromic coating 3A and / or a conductive structured ion storage layer 6A are provided. The term "structured layer" or "structured coating" in the context of the invention refers to a circuit pattern produced by known processes, such as photolithography. More particularly, matrix-like patterns are provided, which allow operation of the electrochromic module 20 in the manner of a display and use for the digitally controlled display of images and symbols.
    [00047] The following example illustrates the production of an inventive electrochromic module. Example 1: A toluene solution containing 1.5 weight percent polymer, prepared by polycondensation of 1,4-bis- (phenylhydroxymethyl) benzene and N, N'-bis- (4-methylphenyl) -N, N ' -diphenylbenzidine is applied to an FTO glass (ie glass equipped with an electrically conductive coating composed of fluorine-doped tin oxide) by means of a rotating coating, forming a homogeneous film about 500 nm thick (after drying ). This is imagined as the working electrode (WE) in the EC module. An ethanolic solution containing 5% by weight of water, 0.2 mol / L of cerium (IV) ammonium (NH4) 2Ce (NO3) 3 and 0.2 mol / L of traisopropyl orthotitanate (Ti (the -propyl) 4) is applied to the other FTO glass by means of a thin layer rotation coating, and dried at 150oC. This is repeated three times and the entire assembly is finally heated to 500oC, forming a mixed CeO2-TiO2 oxide. This is then used in the EC modules as the transparent counter electrode (CE). Two coated FTO glasses (WE and CE) are then combined to render the EC module by means of a hot sealing film. The EC module is finally filled in a sealed container with polymer electrolyte (PVDF-HFP, LiTf2N 0.1 mol / L in EMITf2N) at 90oC through two small holes, and the last ones are subsequently sealed.
    [00048] The cyclic voltamogram of a reversible electrochemical oxidation of the EC polymer in combination with polymer electrolyte (PVDF-HFP, LiTf2N 0.1 mol / L in EMITf2N), demonstrated in an EC module produced according to example 1, is shown in fig. 4 (measuring instrument: Solartron 1285, 15 mV / S). The UV-VIS transmission spectra of the same EC module in the colorless state and with a voltage of +0.4 V (orange) and +0.9 V (blue) are shown in fig. 5 (measuring instrument: Unicam UV 300, measured against air). Chronoamperometric measurements for co-mutation operations between the -1.0 V and +0.4 V (colorless - orange) and - 1.0 V and +0.9 V (colorless - blue) potentials are shown in fig. 6 and fig. 7. Here, very small current densities of 0.2-0.6 mA / cm2 are observed directly after a potential switching. The switching times are obtained from time-dependent electro-optical measurements on the EC module, produced according to example 1, for colorless switching operations - blue (À = 750 nm) (see fig. 8). Table 1 summarizes the electrochromic characteristics for the modules according to example 1 for orange and blue coloring.
    [00049] Optical contrast is defined as the difference in transmission between two states (color) at a particular wavelength. In our case, this is the difference in transmission between the transparent earth state and the orange or blue states. The transmission of the EC module was measured with a Unicam UV 300 UV-VIS spectrometer against air (reference) at room temperature. Transmission is defined as the ratio of the intensity of the light beam transmitted through an electrochromic module to the intensity of the incident light beam as a percentage.
    权利要求:
    Claims (12)
    [0001]
    1. Electrochromic module (10, 20) comprising a first substrate (1), a second substrate (4), the first and / or second substrate (1,4) being electrically conductive or having been provided with an electrically first coating conductive (2), respectively, with a second electrically conductive coating (5), a coating (3) of an electrochromic polymer disposed on the substrate (1) or the first conductive coating (2), an ion storage layer (6) arranged on the substrate (4) or the second conductive coating (5) and an electrolyte (7) electrically connected in series disposed between the electrochromic coating (3) and the ion storage layer (6), the ion storage (6) consists of more than 50% by weight of a material selected from the group comprising tungsten oxide, nickel oxide, cerium oxide, titanium oxide, molybdenum oxide, vanadium oxide (WO3, NiO, CeO2 , TiO2, MoO3, V2O5) or mixtures thereof, characterized by p the fact that the electrochromic polymer (3) is an essentially linear condensation polymer that was formed from a tetraarylbenzidine and an aromatic or heteroaromatic diol and can be switched reversibly under voltage control between more than two redox states, the Condensation polymer is colorless in a redox state and colored in at least two redox states, and where the electrolyte (7) is a polymeric gel electrolyte.
    [0002]
    2. Electrochromic module (10, 20), according to claim 1, characterized by the fact that the electrochromic polymer (3) is an essentially linear condensation polymer formed from a substituted tetrafenylbenzidine and a (hetero) arylene bis-phenylmethanol from generic structural formula (I), (II), (III) or (IV)
    [0003]
    3. Electrochromic module (10.20), according to claim 1 or 2, characterized by the fact that the electrochromic polymer (3) has a glass transition temperature Tg of more than 200oC.
    [0004]
    4. Electrochromic module (10, 20) according to any one of claims 1 to 3, characterized in that the polymeric gel electrolyte (7) comprises at least one cross-linked polymer such as PVDF-HFP, PAN or PMMA, at least one ionic liquid such as 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulfonyl) imide, propylene carbonate, propylene carbonate / ethylene carbonate / diethyl carbonate mixtures and at least one lithium salt such as lithium bis (trifluoromethanesulfonyl) imide (LiTF2N), lithium trifluoromethanesulfonate (LiTFO) or LiClO4.
    [0005]
    5. Electrochromic module (10.20), according to any one of claims 1 to 4, characterized by the fact that the ion storage layer (6) consists of an extension of more than 80% by weight of a selected material from the group comprising tungsten oxide, nickel oxide, cerium oxide, titanium oxide, molybdenum oxide, vanadium oxide (WO3, NiO, CeO2, TiO2, MoO3, V2O5) and their mixtures, preferably mixed CeO2- oxide TiO2.
    [0006]
    6. Electrochromic module (10.20), according to any one of claims 1 to 5, characterized by the fact that the electrochromic polymer (3) can be switched under voltage control between three redox states in which it preferably according to the redox state, it assumes the color states of colorless, orange or blue.
    [0007]
    7. Electrochromic module (10, 20), according to any one of claims 1 to 6, characterized by the fact that with the application of a voltage in the range of 0.35 to 0.45 V it has a wide absorption band having a maximum absorption in the wavelength range of 1200 to 1400 nm, with the optical contrast at maximum absorption being 13% to 15%.
    [0008]
    8. Electrochromic module (10.20), according to any one of claims 1 to 7, characterized by the fact that the number of switching cycles with an electrochromic contrast in the range of 90 to 100%, based on the starting value, is greater than 20,000.
    [0009]
    9. Electrochromic module (10.20), according to any one of claims 1 to 8, characterized by the fact that the electrochromic efficiency r = log (optical density / charge density Q) is greater than 600 cm2 / C, preferably greater than 800 cm2 / C.
    [0010]
    10. Electrochromic module (10.20), according to any one of claims 1 to 9, characterized by the fact that it has an electrochromic contrast greater than 40%, preferably greater than 60%, precisely with radiation of a wavelength 480nm or 750nm.
    [0011]
    11. Electrochromic module (10.20) according to any one of claims 1 to 10, characterized in that the switching time from blue to colorless is less than 2 s and the switching time from colorless to blue is less than 7 s.
    [0012]
    12. Electrochromic module (10.20), according to any one of claims 1 to 11, characterized in that the electrochromic polymer (3) forms a homogeneous layer having a thickness of 5 to 500 nm, preferably 50 to 500 nm , and especially 200 to 500 nm.
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    同族专利:
    公开号 | 公开日
    WO2012119734A1|2012-09-13|
    BR112013022298A2|2016-12-06|
    CN103582844A|2014-02-12|
    JP6246594B2|2017-12-13|
    KR101966612B1|2019-04-09|
    EP2681620B1|2018-02-21|
    CN103582844B|2016-10-26|
    EP2681620A1|2014-01-08|
    US20130335800A1|2013-12-19|
    WO2012119734A8|2013-11-21|
    ES2665506T3|2018-04-26|
    RU2587079C2|2016-06-10|
    DE102011013132A1|2012-09-06|
    KR20140008426A|2014-01-21|
    IN2013CN06515A|2015-08-07|
    US9164345B2|2015-10-20|
    RU2013138016A|2015-04-10|
    JP2014510944A|2014-05-01|
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    法律状态:
    2018-12-18| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-01-12| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-03-16| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102011013132A|DE102011013132A1|2011-03-04|2011-03-04|Stable electrochromic module|
    DE102011013132.9|2011-03-04|
    PCT/EP2012/000932|WO2012119734A1|2011-03-04|2012-03-02|Stable electrochromic module|
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