The present application is the US national stage of International Application PCT/EP2010/057981 filed on Jun. 8, 2010, which in turn, claims priority to German Patent Application No. 10 2009 026 148.6 filed on Jul. 10, 2009.
The invention relates to an electrochromic layer structure, an electrochromic device, a method for production of an electrochromic layer structure as well as a use of an electrochromic layer structure and an electrochromic device.
Windows are an important component in buildings. Whereas, in the past, windowpanes served merely the purpose of a clear view toward the outside, nowadays substantially higher demands are placed on glazings. For one thing, glazed areas should serve for ideal thermal insulation of interior spaces; however, for another, they should also ensure that, because of the glazing, when the sun shines in, interior spaces are heated only to a desirable level. A possible control of the admission of light through glazed areas can be regulated, for example, by movable blinds. Another possibility is offered by glazings that change their optical properties such as transparency and reflectivity at the touch of a button or independently. Such switchable glazings offer architects greater design flexibility for glazed areas without requiring movable parts in front of or within a fagade.
Glazings that change their optical properties at the touch of a button or independently also include electrochromic glazings. Electrochromic glazings operate on the principle that the optical properties of electrochromic layers change by means of absorption and discharge of charge carriers. When a current flows, an exchange of charge carriers occurs and the electrochromic layer changes its permeability to sunlight.
Typically, electrochromic glazings include an active layer that is surrounded by transparent electrodes. Through application of an external voltage, charge carriers are transported into the active layer causing the active layer to change its transparency to visible light. If a voltage of the opposite polarity is then applied, the charge carrier migration is reversed such that the original transparency is restored. The active layer includes an ion-conducting electrolyte and electrochromic material. The electrochromic material changes its transmission properties for electromagnetic radiation by changing its oxidation state. The electrolyte can consist of an inorganic material as is disclosed in EP 0 867 752 and EP 0 831 360. However, the electrolyte can also consist of an organic material, which is described in EP 0 253 713 and EP 0 382 623. The active layer can be present completely or partially in a solid or liquid state. An electrolyte with solid and liquid components is disclosed, for example, in WO 2008/084168. If the active layer and the electrodes include polymer material, this combination is referred to as an all-polymeric electrochromic system. Such systems are, for example, known from U.S. Pat. No. 6,747,779 B1.
It is problematic that a complete transparency change of the active layer can require as much as several minutes. This represents no problem with simple building glazings; however, it is unacceptable for use, for example, in motor vehicles, aircraft, and rail vehicles. Here, it must be guaranteed that an immediate increase in transparency of the electrochromic glazing takes place at the time of a spontaneous external change from bright to dark, as occurs, for example, when driving into a tunnel. The same is true for emergency situations in which it is required that maximum transparency of electrochromic glazings, e.g., in motor vehicles, be guaranteed within split seconds.
One of the reasons for a relatively slow tint transition process of the active layer in electrochromic glazings is the low electrical conductivity of the electrodes that limits a possible flow of current for the change in transparency of the active layer.
To address this problem, U.S. Pat. No. 6,747,779 B1 discloses additionally providing one of the electrodes with an electrically conductive network. This network is produced with metal wires or with the use of a paste. The paste contains silver particles and gas frits.
However, the use of the conductive paste has the disadvantage that the methods for stabilization of the paste require high process temperatures. The high temperatures are required, in particular, to melt the glass frits and/or to sinter the silver particles. Through the method, the active layer, which is sensitive to high temperatures, is attacked.
Alternative low-temperature methods for stabilization and curing of pastes are, on the other hand, very time-consuming.
The formation of an electrically conductive network with metal wires is material-intensive since the application of finished metal wires requires a greater amount of metal material than is necessary for the required electrical conductivity of the network.
With the formation of electrical networks using metal wires, it must also be noted that the selection of possible network geometries is reduced.
The object of the invention is to provide an improved electrochromic layer structure, an improved electrochromic device, and an improved method for production of an electrochromic layer structure.
In addition, the object of the invention is to find a new use of an improved electrochromic layer structure and an improved electrochromic device.
The objects of the invention are accomplished in each case through the characteristics of the independent claims. Preferred embodiments of the invention are indicated in the dependent claims.
According to the invention, an electrochromic layer structure with at least one active layer is provided, wherein the layer structure has at least two electrodes, and at least one of the electrodes has an electrically conductive network of conductor tracks, and the conductor tracks contain nanoparticles.
These nanoparticles can have a diameter of 1 nm to 500 nm. However, the nanoparticles have a diameter of 5 nm to 100 nm, and, particularly preferably, the nanoparticles have a diameter of 10 nm to 30 nm.
The nanoparticles contain metals and/or carbon compounds. Preferably, the nanoparticles contain silver, copper, aluminum, carbon black (conductive carbon black), and/or carbon nanotubes as well as mixtures thereof.
The use of nanoparticles for the formation of the conductor tracks has the advantage that with this particle size, the process temperature required for the printing process for stabilization of the conductor tracks or sintering is reduced. Thus it is possible, with a diameter distribution in the range below 100 nm, to reduce the process temperature to as low as 70° C. In this temperature range, the active layer is not temperature sensitive since the active layer is designed to withstand temperatures above 70° C. in a laminate of panes with maximum incident sunshine.
For protection of the active layer and of the electrodes against external influences, such as moisture or mechanical stress, the electrochromic layer structure has transparent protective layers and/or protective panes.
Preferably, the protective layer includes silicon nitrides, oxides such as silicon oxide, silicon nitride or zinc oxide, indium oxide, tin oxide, and/or mixtures thereof, with a preferred thickness of 5 nm to 500 nm.
According to a preferred embodiment of the invention, the protective pane of the layer structure can also include germanium, silicon, silicate glasses such as soda lime glass, borosilicate glass, sapphire, or polymers such as polystyrene, polyamide, polyester, polyvinyl chloride, polycarbonate, ethylene vinyl acetate, plasticized polyvinyl butyral, polyimide, polyethylene terephthalate, polyethylene, polypropylene, polyurethane, ionomers, and/or polymethyl methacrylate, copolymers and/or combinations thereof. The protective panes have a preferred thickness of 0.01 mm to 25 mm. The protective panes can be rigid panes or mechanically flexible and have the nature of film. Protective panes have the advantage that they encapsulate the active layer and the electrode material against external environmental influences and, in particular, protect against mechanical effects.
The protection of the active layer and/or of the electrodes can further be improved by an additional protective layer lying between the active layer and the protective pane containing argon, xenon, nitrogen, air, and/or mixtures with a pressure of 1000 Pa to 200,000 Pa. A particularly well-suited construction of a gaseous protective layer is known with multipane insulating glazings.
Preferably, the network of conductor tracks formed by nanoparticles is developed between the active layer and the protective layer and/or between the active layer and the protective pane.
This enables the use of various production methods, wherein, preferably, the conductor track network is applied directly on the active layer, the conductor track network is applied on the electrode, or the conductor track network is applied on an optically transparent and conductive protective layer. This opens a broad field of alternative production methods for electrochromic layer structures that can be flexibly adapted to physical conditions and also to workflow-related conditions. Thus, it is to be anticipated that with direct application of the electrically conductive network on the active layer, a charge carrier exchange in the active layer is greatly increased such that such a design is suitable, in particular, for electrochromic layer structures that are to be switched extremely quickly. It is also conceivable to produce the active layer together with the electrodes in a workflow and not to apply the conductor track network until after that. In this case, there is the possibility of the flexible choice of the subsequent application of the conductor track network on one of the electrodes or on a protective layer that is optically transparent in the range of visible light, whereby, in this case, the network of conductor tracks is located between the electrode and the protective layer.
It is also possible to design the electrochromic layer structure with at least two active layers lying one above the other and with intermediate electrodes lying between them. This embodiment has the advantage that the active layers can be switched independently of each other.
According to another embodiment of the invention, the electrically conductive network is optically transparent when viewed macroscopically. “Optically transparent when viewed macroscopically” means that the electrically conductive networks of conductor tracks can, in themselves, be microscopically opaque; but because of their small share of the area relative to the total area, they appear optically transparent when viewed macroscopically. Optical transparency includes the technically usable electromagnetic radiation spectrum, preferably, the ultraviolet, visible, and infrared radiation spectrum. Thus, the electrochromic layer structure can be used even in glazings that require the best possible visibility, without restriction yet capable of being darkened, for permanent visibility while operating means of transportation such as aircraft, automobiles, and trains.
According to one embodiment of the invention, the conductor tracks have a width between 1 μm and 10 mm, with the conductor tracks having a distance of 1 μm to 50 mm between them. Preferably, the conductor tracks are, however, dimensioned with regard to their width and spacing such that, with the minimum possible material outlay for the formation of the conductor tracks, adequately high electrical conductivity for charge carrier transport and adequately high optical transparency can be guaranteed.
According to one embodiment of the invention, the electrically conductive network has conductor tracks with different layer thicknesses. Thus, the conductor tracks of the network have different electrical conductivities. An advantage of this embodiment consists, in particular, in that because of the different electrical conductivity, different regions of the active layer can be actuated differently.
According to another embodiment of the invention, the nanoparticles are carbon nanoparticles, with the carbon nanoparticles being carbon nanotubes and/or carbon black. Carbon black consists of small particles with a typical size range between 10 nm and 100 nm. With the use of carbon black, so-called conductive carbon black, which has particularly good electrical conductivity, can be used as nanoparticles for conductor tracks.
The use of carbon nanotubes has the advantage that they have high electrical conductivity because of their high aspect ratio, diameter to length. Thus, an extremely small quantity of carbon nanotubes suffices to, nevertheless, guarantee high electrical conductivity of the conductor tracks formed from them.
Alternatively, it is also possible for the nanoparticles in the form of a composite material with a plastic or silicate glass to form the conductor tracks. Such plastics can be polyacrylates, epoxides, and/or polyaniline as well as copolymers and/or combinations thereof. Through the additional use of plastics as carriers of the conductor tracks, their mechanical stability is increased for one thing. For another, through the use of conductive plastics, such as polyaniline, the electrical conductivity of the conductor tracks formed by nanoparticles is further increased. Thirdly, the use of plastics in the conductor tracks, which encapsulate the nanoparticles relative to the active layer, for example, serves to prevent direct spatial contact between the active layer and the nanoparticles. Thus, ion-conductive materials, which would enter into a chemical or electrochemical reaction with the nanoparticles without encapsulation of the nanoparticles can also be used as the active layer. Thus, the flexibility with regard to the selection of the ion-conductive materials used in the active layer is increased.
In another aspect, the invention relates to an electrochromic device with the layer structure according to the invention in electrical contact with a control unit.
In a preferred embodiment, the electrochromic device includes at least two protective panes. Such an electrochromic device can be an electrochromic glazing.
According to another embodiment of the invention, at least one protective layer of the electrochromic layer structure is formed by an external protective pane or an external protective pane is formed by a protective layer of the electrochromic layer structure. It is possible, through appropriate selection of the optically transparent protective layer material in the use of the electrochromic device as window glazing, to do without an additional glass pane. Plastic materials can be used that are, for one thing, optically transparent in the range of visible light, and, for another, have high mechanical hardness, but without having the weight of conventional window glazings. This yields the possibility of the production of electrochromic glazings with substantially lower weight than is the case with glazings customary in the trade.
The protective pane can be constructed in the electrochromic device as a composite pane made of a plurality of layers and can preferably include a polymer layer as a binding agent. Particularly preferably, the layer structure with an additional protective pane as a laminated glass can form an electrochromic device.
This electrochromic device can be a window pane and, preferably, a laminated glass pane, wherein the surfaces are formed from silicate glass and/or polymers.
In one embodiment of the electrochromic device, it is a double-insulating or multi-insulating glazing, wherein the electrochromic layer structure is located on internal and/or external window panes of the insulating glazing. A gaseous protective volume of the layer structure is advantageous, particularly with the use of the electrochromic layer structure in double-insulating or multi-insulating glazings as an electrochromic device since the insulating glass construction provides a protective volume. In this embodiment, the protective volume also reduces the passage of heat through the glazing and has a thermal insulating effect.
In another aspect, the invention relates to a method for production of an electrochromic layer structure with at least one active layer, wherein the layer structure has two electrodes, and the method comprises the steps of the application of a network of nanoparticles on at least one of the electrodes and the step of the heating of the network of nanoparticles to form an electrically conductive network of conductor tracks.
According to one embodiment of the invention, the application of the networks of nanoparticles occurs, preferably, through a printing method, such as screenprinting, engraving cylinder printing, and, particularly preferably, inkjet printing, aerosol jet printing, pulse jet printing, and/or roller rotation printing methods, such as flexography.
Through the method according to the invention, any geometries can be printed on areas. Contact-free printing is also possible with methods according to the invention. It is also possible to print a conductive network between the active layer and the electrode. Preferred geometries are, for example, lines and curves arranged parallel or antiparallel, lines or curves with cross connections, regular or irregular net-like structures, contiguous areas with regular or irregular recesses, as well as noncontiguous rectangles or ellipsoids.
The selection of the suitable liquid depends on various criteria, such as process temperature for stabilization of the networks, aggregation behavior of the nanoparticles in a liquid as well as, in particular, with the selection of liquid plastics as the liquid, the later use of the hardened plastic as protective conductive encapsulation of the nanoparticles.
According to another embodiment of the invention, the application of the network of nanoparticles takes place through application of a dispersion, wherein the dispersion comprises the nanoparticles and a liquid and the liquid is water and/or an organic solvent and/or a liquid plastic.
The size of the devices according to the invention can vary broadly and is determined by the respective purpose for use in the context of the use according to the invention. Thus, the devices according to the invention can have dimensions on the order of a few centimeters up to several meters. In particular, the devices that are planar or slightly or greatly bent or curved in one or a plurality of spatial directions can have an area on the order of 100 cm2 to 25 m2, preferably, >1 m2 or PLF (3.21 m×6.0 m=19.26 m2), which is the “standard” of the glass industry. The devices according to the invention can also have areas as they customarily have in covers for headlights, windshields, side windows, rear windows, and glass roofs for motor vehicles or large-area panes, in particular as are used in the building sector.
According to another embodiment of the invention, the stabilization or sintering of the network of nanoparticles into conductor tracks is accomplished by thermal conduction and electromagnetic radiation in ovens, but, preferably, through infrared radiation and ultraviolet radiation and, particularly preferably, through laser irradiation and/or microwave irradiation. The use of laser irradiation has the advantage that by targeting a focused laser beam at the desired network structure of nanoparticles exclusively on the desired spatial network structures on which the laser beam strikes the nanoparticles, a process of stabilization of the network and thus, as the case may be, a bonding of the nanoparticles to the electrodes and/or the active layer also occurs. Nanoparticles that which lie outside the desired network structure traveled by the laser beam are not included in the heating process such that no curing and no direct processing occur here. A subsequent washing process thus enables removing nanoparticles that were not struck by the laser beam defining the network. Thus, in a simple manner, a well-defined conductive network of nanoparticles can be created.
In addition, embodiments of the invention are explained in detail with reference to the drawings. They depict:
In the following, elements similar to each other are labeled with the same reference characters.
The electrochromic control unit 112 serves, as a result of the application of a voltage between the electrodes 102 and 104, as a transparency control of the active layer relative to incident light. The electrode 104 is an anode, and the electrode 102 is a cathode. As a result of the application of a positive voltage to the anode 104 and a negative voltage to the cathode 102, ion transport through the active layer 100, which includes an ion-conductive polymer, occurs. The cathode 102 contains tungsten oxide. The anode 104 contains hydrogen ions. As a result of the application of voltage between the anode and cathode, hydrogen ions migrate through the ion-conductive polymer into the cathode 102 and form color centers there with tungsten oxide that absorb or reflect incident light. When a voltage of the opposite polarity is then applied, this effect is reversed such that decolorization of the cathode 102 occurs.
The ion migration depends greatly on the selection and thickness of the active layer 100, on the one hand, and also on the material selection and the thickness of the cathode 102. The problem emerges here that with overly thin dimensioning of the cathode 102 whose optical transparency is high but the electrical conductivity is so low that an electrochromatic coloration or decoloration process takes considerable time because of the low charge transport. By contrast, if the conductivity of the cathode layer 102 is increased by increasing its thickness, the electrochromatic transparency change process can be accelerated, but at the cost of a reduced maximum transparency and of the increased thickness and, with it, of the permeability to light of the layer 102.
To remedy this problem, the network 110 of conductor tracks in
The conductor tracks 110 are, preferably, arranged such that when viewed macroscopically, the network formed by the conductor tracks is optically transparent. This can be realized through an extremely thin dimensioning of the conductor tracks with a width of less than 10 μm and with a large distance between them, preferably, more than 1 mm.
As is discernible from
An alternative embodiment thereto is depicted in
In an enlargement of the electrically conductive network of conductor tracks 110, the nanoparticles 300 depicted in
In the enlargement of
It should be noted that the method for application of the network is suitable both to apply the network on the cathode and on the anode in the form of two separate networks.
An alternative embodiment of a method for production of an electrochromic layer structure is depicted in the flow diagram of
After the protective pane is prepared in step 500, the network is applied on the protective pane in step 502. The network is again heated in step 504, which results in curing, sintering, or general stabilization. After that, in step 506, an electrode is applied on the network thus formed, whereupon, in step 508, an active layer is applied on the electrode. And finally, in step 510, an additional electrode is applied on the active layer.
Alternatively to the steps depicted in
The electrodes 102 and 104 as well as the intermediate electrode have electrically conductive networks 110. The effect of the electrically conductive networks 110 corresponds to the observations of the exemplary embodiment of
In
Another embodiment is depicted in
An alternative embodiment thereto is depicted in
An alternative embodiment of the layer structure according to the invention is depicted in
Another alternative embodiment is depicted in
Number | Date | Country | Kind |
---|---|---|---|
10 2009 026 148 | Jul 2009 | DE | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
---|---|---|---|---|
PCT/EP2010/057981 | 6/8/2010 | WO | 00 | 1/31/2012 |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO2011/003686 | 1/13/2011 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
4844591 | Arribart et al. | Jul 1989 | A |
5229040 | Desbat et al. | Jul 1993 | A |
5293546 | Tadros et al. | Mar 1994 | A |
6496295 | Wittewer et al. | Dec 2002 | B1 |
6747779 | Morin et al. | Jun 2004 | B1 |
6791737 | Giron et al. | Sep 2004 | B2 |
7193763 | Beteille et al. | Mar 2007 | B2 |
20060163744 | Vanheusden et al. | Jul 2006 | A1 |
20060191215 | Stark | Aug 2006 | A1 |
20070153353 | Gruner | Jul 2007 | A1 |
20100027098 | Piroux et al. | Feb 2010 | A1 |
20100028633 | O'Rourke et al. | Feb 2010 | A1 |
20110273085 | Garbar et al. | Nov 2011 | A1 |
Number | Date | Country |
---|---|---|
0253713 | Jan 1988 | EP |
0381360 | Aug 1990 | EP |
0382623 | Aug 1990 | EP |
0867752 | Sep 1998 | EP |
60011884 | Jan 1985 | JP |
2006312673 | Nov 2006 | JP |
2008235035 | Oct 2008 | JP |
2008084168 | Jul 2008 | WO |
Entry |
---|
PCT International Search Report issued for PCT/EP2010/057981 filed Jun. 8, 2010 in the name of Saint-Gobain Glass France. |
PCT Written Opinion mailed on Sep. 14, 2010 for PCT Application No. PCT/EP2010/057981 filed on Jun. 8, 2010 in the name of Saint-Gobain Glass France. |
Number | Date | Country | |
---|---|---|---|
20120134004 A1 | May 2012 | US |