CN101322069B - Transparent electrode for an electrochromic switchable cell - Google Patents
Transparent electrode for an electrochromic switchable cell Download PDFInfo
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- CN101322069B CN101322069B CN2006800234722A CN200680023472A CN101322069B CN 101322069 B CN101322069 B CN 101322069B CN 2006800234722 A CN2006800234722 A CN 2006800234722A CN 200680023472 A CN200680023472 A CN 200680023472A CN 101322069 B CN101322069 B CN 101322069B
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Abstract
An electrochromic switchable transparency, e.g. a window and/or a mirror includes an electrochromic switchable medium between a pair of electrode assemblies. At least one of the electrode assemblies is transparent to visible light and includes an electrode over a surface. In one nonlimiting embodiment of the invention, the electrode has two electrically conducting layers and a bridging layer between and interconnecting the two electrically conducting layers. In one nonlimiting embodiment, the bridging layer includes a high electrically resistance connecting layer to provide the electrode with a heating layer to heat the surface and/or a current conducting layer to pass current to the medium. In another nonlimiting embodiment, the bridging layer includes an electrically connecting layer to pass current to electrically enhance the first electrically conductive layer. In another nonlimiting embodiment, the electrically conducting layers are silver films to reduce infrared transmission through the first electrode assembly.
Description
The cross reference of related application
The application is called " A Vision Panel Having a Multi-layer Primer " U.S. Patent application the 11/472nd with the name of submitting to simultaneously, No. 331, be called " An Electrochromic Vision PanelHaving a Plurality of Connectors " U.S. Patent application is correlated with for the 11/472nd, No. 330 with name.The full content of these applications is incorporated into this by reference.
Technical field
The present invention relates to be used for the transparency electrode of electrochromic switchable cell, relate more specifically to have the coating lamination transparency electrode of (coating stack), this coating lamination has by conductive layer or such as the separated pair of conductive layer of the resistive formation of dielectric layer.
Background technology
Technology describes in detail
When expectation changes the transmission of visible light that passes through glass or windowpane, can use electrochromism conversion glass usually.For example but do not limit this argumentation, conversion glass is used as the windshield and/or the side window of aircraft, thinks that operating personnel and/or the passenger in the aircraft provides the ability that increases or reduce the transmission of visible light of glass.
One type electrochomeric glass or system comprise anode compound and the cathode compound in the solution that is in together between a pair of isolated electrode assemblie.The system of another kind of type comprises the polymkeric substance with negative electrode variable color between a pair of isolated electrode assemblie, the polymkeric substance of (ionicallyconductive) polymkeric substance of electrical isolation but ionic conduction and the polymkeric substance of anode variable color.Also have a kind of system to be included in ionic conduction between a pair of isolated electrode assemblie but the inorganic layer of electrical isolation.For the more detailed argumentation of above-mentioned electrochromic system, can be referring to U.S. Patent No. 5,202,787; 5,805,330; 6,643,050 and 6,747,779.As skilled in the art to understand, for EC mirror, at least one electrode assemblie is transparent, and for electrochomeric glass, preferred two electrodes all are transparent.
Electrode assemblie in a kind of configuration comprises the electrode that is installed on the glass sheet.The pair of electrodes assembly is mounted with the relation of space, and wherein, electrode electrically contacts toward each other and with interelectrode electrochromic media.Electrode is connected on the circuit, thereby when electrifying electrodes, voltage is applied on the electrochromic media and makes the medium variable color.For example but do not limit this argumentation, when electrochromic media is applied in voltage, its meeting deepening also begins absorbing light to reduce the visible number percent that sees through the visible light of electrochromic media, with when electrochromic media is de-energized, it can brighten to increase the number percent of the visible light that sees through electrochromic media.The voltage that is applied to medium is depended in the reduction of the number percent of the visible light by medium, and for example when the voltage that applies increased, the number percent that sees through the visible light of medium reduced.For more detailed argumentation about the operation of electrochromism conversion glass, can be referring to above-mentioned U.S. Patent No. 5,202,787; 5,805,330; 6,471,360 and 6,643,050.
In the scope of the electrochromic media glass of transmission of visible light, the electrochromism conversion medium is the function of some parameters of describing the above-mentioned patent from the conversion rate that is up to minimum transmission of visible light.For example but do not limit this argumentation, a parameter is the conductivity of electrode, for example contacts the sheet resistance of the electrode of electrochromism conversion medium.This sheet resistance is that what to measure between 2 on the electrode surface of being appointed as the contact electrochromic media is the electrode resistance of unit with the every square of ohm (ohms per square).The step that is used for the sheet resistance of definite electrode is well known in the art, need not further argumentation.
As skilled in the art to understand, for the given voltage that applies, along with the reduction of the sheet resistance of electrode, the conversion time from maximum visible transmission value to minimum visible transmission value reduces, and vice versa.The minimizing of conversion time is the result of the electric current of electrode and electrochromism conversion medium increase that flows through.In general, in order to obtain uniform distribution of current between electrode, the expectation electrode has low sheet resistance, for example less than 10 ohm of every squares.
This area recognizes that also temperature change is influential to conversion time, and for example along with temperature reduces, conversion time prolongs, and vice versa.
The argumentation of existing available techniques
U.S. Patent No. 5,805,330 disclose the material of the electrode of the electro-optical device that can be used as the photoelectricity power supply.These materials comprise the extra play (for example IMIMI) of the tin oxide of doped with fluorine, the indium oxide of doped tin (below be also referred to as " ITO "), thin metal layer, ITO/ metal/ITO (following this combination is also referred to as " IMI ") and metal and ITO.U.S. Patent No. 6,747,779 disclose the electrode of ITO/ silver/ITO, silver/ITO and dielectric/silver/ITO, have the thin layer of the metal of the insertion portion oxidation of choosing wantonly at the interface at silver-colored ITO.
U.S. Patent No. 6,561,460 disclose a kind of antifog electrochromism pane assembly, be included in first substrate that has conductive coating on the outside first surface and on inner second surface, have second conductive coating, and with isolated second substrate of first substrate, wherein second substrate externally has the 3rd conductive coating on the first surface.Thereby the outside first surface of the inside second surface of first substrate and second substrate is faced with the end relation that is spaced apart from each other and is limited the space with electrochromic media betwixt.Electric current is applied to first conductive coating to heat this first conductive coating, and this prevents the pane module atomizing, and voltage is applied on the second and the 3rd conductive coating to change the transmissivity of electrochromic media.
Although U.S. Patent No. 6,561,460 antifog electrochromism pane assembly is acceptable at its predetermined purpose, also has restriction.More specifically, on the two sides, all has the necessary handled of sheet of coating, to prevent surface distress to one or two coating surface.
Such as will be appreciated, a kind of electrode advantageously is provided, this electrode provides the equally distributed electric current by electrochromic media, provide the one or more outside surfaces that help heat electrochromism conversion glass, and/or strengthen the sunshade of electrochromic media, and be not limited to the transparency electrode of existing electrochomeric glass.
Summary of the invention
The present invention relates to one type article, it has and isolated first electrode assemblie of second electrode assemblie, and the medium between first and second electrode assemblies.This dielectric response electric excitation and change number percent through the visible light of this medium, for example, this medium is the electrochromism conversion medium (electrochromic switchable medium) that is selected from liquid, solid, gel or its combination.In a non-limiting example of the present invention, these article are the electrochromism conversion glass that has at least one transparent electrode assemblie of the wavelength in the electromagnetism level range of 400~700 nanometers (for example first electrode assemblie).
In a non-limiting example of the present invention, first electrode assemblie has the electrode that is defined as first electrode; Second electrode assemblie has the electrode that is defined as second electrode, and first and second electrodes are in the relation that faces with each other, and its medium is between first and second electrodes.First electrode assemblie has first first type surface in the face of medium, the first surface of glass sheet for example, and wherein first electrode is between first first type surface and medium.First electrode also comprises first conductive layer between the medium and first first type surface, and first first type surface is spaced apart and second conductive layer between first conductive layer and medium, be spaced apart from each other and contact first and second contact parts of first conductive layer, bus-bar for example, wherein, first and second contact parts and first conductive layer provide first conductive path, and the 3rd contact part that contacts second conductive layer.The 4th contact part contacts second electrode, and wherein, third and fourth contact part, second conductive layer, medium and second electrode provide second conductive path.
Other non-limiting example of the present invention comprises the glass sheet with opposing second surface, and wherein at least one surface of glass sheet has the coating in the group that is selected from hydrophobic coating, hydrophilic coating, anti-solar control coating and combination thereof; Thereby between the electrode assemblie and the spacing frame of the sealing that is connected with electrode assemblie hold medium so that seal cavity to be provided between electrode assemblie; Article are selected from following group: the A) glass of the type of vehicle of selecting from following group: a) land craft of selecting in the group of automobile, truck, car, motorcycle, train and combination thereof; B) aircraft; C) spacecraft; D) marine communication means; E) underwater vehicle; And f) its combination; B) window of the structure of from following group, selecting: a) residential building; B) commercial building; C) oven door; D) door for microwave oven; E) refrigerator doors; And f) its combination; C) mirror; D) vehicles rearview mirror; E) vehicles side-view mirror; F) vehicle glass of from following group, selecting: windshield, side window, roof window, the vehicles windowpane of rear window and combination thereof and aircraft windshield window, and G) and the combination.
In another non-limiting example of the present invention, electric excitation is that unit is measured with the volt that is applied between the electrode assemblie, and dielectric response electric excitation, change one of in the following manner the number percent of the visible light that sees through this medium: along with the increase of voltage between the electrode assemblie, the percent transmittance by medium reduces; Along with the reduction of voltage between the electrode assemblie, by the percent transmittance increase of medium; With the increase of voltage between the electrode assemblie, by the percent transmittance increase of medium; With the reduction of voltage between the electrode assemblie, by the percent transmittance reduction of medium, and combination.
In another non-limiting example of the present invention, because voltage is applied between first and second conductive components, so first conductive layer and surface are by electrical heating.
In another non-limiting example of the present invention, the high resistance articulamentum is between first and second conductive layers, this articulamentum has predetermined impedance to the electric current that flows along first conductive layer, makes the electric current less than 50% that moves along first conductive path arrive second conductive layer by this articulamentum.It is electrical isolation or dielectric layer that the present invention imagines this high resistance articulamentum.
In another non-limiting example of the present invention, the conduction articulamentum is between first and second conductive layers, this articulamentum has predetermined impedance to the electric current that flows along first conductive layer, makes the electric current greater than 50% that moves along first conductive path arrive second conductive layer by this conduction articulamentum.It is conductive metal oxide layer that the present invention imagines this conduction articulamentum.
In another non-limiting example of the present invention, second electrode assemblie has the first type surface that is defined as in the face of second first type surface of medium, wherein second electrode is between second first type surface and medium, and second electrode comprises the conductive layer that is defined as the 3rd conductive layer between the medium and second first type surface; And the 3rd conductive layer is spaced apart and be defined as the conductive layer of the 4th conductive layer between the 3rd conductive layer and medium.The 4th contact part contacts the 4th conductive layer, and the spaced the 5th contact the 3rd conductive layer with the 6th contact part, and wherein the 5th and the 6th contact part and the 3rd conductive layer provide the 3rd conductive path.
Other non-limiting example of the present invention comprises (1) dielectric layer between first conductive layer and substrate surface, dielectric layer between the substrate surface and first conductive layer comprises supporting layer, for example zinc stannate film, and metal contact layer (for example zinc oxide film) is to strengthen the electric conductivity of metal level (for example silver layer); (2) between first and second conductive layers with when the high resistance articulamentum that makes electric current along second path flow is crossed medium time heating first surface; (3) between first and second conductive layers to strengthen along the conductive layer of the electric current of second path movement; (4) first conductive layers and/or comprise supporting layer; the articulamentum of zinc stannate film for example; and (5) each conductive layer includes the protective seam on metal level and the metal level; randomly; protective seam is an anoxic pottery sputtered film; indium oxide tin film for example, and comprise conduction sputter ceramic membrane, for example indium oxide tin film that contains the oxygen of Duoing on the anoxic ceramic membrane than anoxic pottery sputtered film.
Other non-limiting example of the present invention comprises the first and the 3rd contact part of the negative or positive electrode terminal that connects direct supply, the second and the 4th contact part with negative pole that is connected respectively to power supply or positive terminal, or first and second contact part be connected in first direct supply, and third and fourth contact part is connected in second direct supply.
The invention still further relates to the article that improve type, the type has and isolated first electrode assemblie of second electrode assemblie, and the medium between first and second electrode assemblies, this dielectric response electric excitation and change number percent through the visible light of medium, this improvement comprises at least one electrode assemblie, and described electrode assemblie comprises a surface; Be positioned at first zinc stannate layer on this surface; Be positioned at first zinc oxide film on this first zinc stannate layer and the metal level on this first zinc oxide film, the silverskin on the zinc oxide film for example is positioned on this silverskin or diaphragm thereon and be positioned on the protective seam or indium oxide tin film thereon.
The invention still further relates to the method for operation electrochromic switchable cell type, the electrochromic switchable cell of the type comprises and isolated first electrode assemblie of second electrode assemblie, and the electrochromism conversion medium between first and second electrode assemblies, this method may further comprise the steps: first electrode assemblie is provided, first electrode assemblie have first conductive layer spaced apart with first type surface and that contact with the electrochromism conversion medium and between first conductive layer and first type surface and with first conductive layer and isolated second conductive layer of electrochromism conversion medium; And, make electric current pass through first and/or second conductive layer in seclected time.
Description of drawings
Fig. 1 is the cross-sectional side view that lifts of the non-limiting example of electrochromism conversion glass of the present invention.
Fig. 2 is a view like the view with Fig. 1, and wherein the electrochromism conversion glass shown in Fig. 1 revolves and turn 90 degrees.
Fig. 3 is the side view that lifts of the non-limiting example of electrode assemblie of the present invention.
Fig. 4 is like the view with Fig. 3, illustrate in greater detail the view of another non-limiting example of electrode assemblie of the present invention.
Fig. 5 is like the view with Fig. 1, show another non-restrictive example view of electrochromism conversion glass of the present invention.Fig. 5 comprises Fig. 5 A and Fig. 5 B, and they are zoomed-in views of the non-limiting example that is connected with the bus-bar of electrode of the present invention.
Fig. 6 is the synoptic diagram of non-limiting example that can use the electronic circuit of the electrode power supply of thinking the electrochromism conversion glass shown in Fig. 5 in the present invention practice.
Fig. 7 is the view that another non-limiting example of electrochromism conversion glass of the present invention similarly is shown with view 1.
Fig. 7 A and Fig. 7 B are that the electrode that is connected in Fig. 7 is thought the synoptic diagram according to the non-limiting example of the electronic circuit of the present invention of electrode power supply of the present invention.
Fig. 8 is the cross-sectional side view with aircraft glass of electrochromism conversion glass of the present invention.
Fig. 9 is the cross-sectional side view with electrochromism transformation glass of electrode of the present invention.
Embodiment
Space or direction term as used herein, as " inside ", " outside ", " left side ", " right side ", " on ", D score, " level ", " vertically " etc., relate to the present invention as shown in the figures.But, be appreciated that the present invention can take the orientation of plurality of optional, thereby these terms are not thought determinate.And all numerals of the expression size of using in instructions and claims, physical characteristics etc. can be understood as in all examples to be revised with term " about ".Therefore, unless be designated as reverse situation, the numerical value that proposes in instructions and claims ideal behavior that can reach out for and changing below according to the present invention.At least, but the application that is equal to replacement that does not limit the scope of the claims, each digital parameters should be explained according to the quantity of the significant figure that write down with by the technology of rounding off of routine at least.In addition, disclosed all scopes will be understood to include any and all subranges that comprise in the literary composition in the literary composition.For example, the specialized range of " 1 to 10 " will be understood that any and all subranges that are included in (and comprising endpoints thereof) between minimum value 1 and the maximal value 10; That is to say, originate in minimum value 1 or 1 above and end at maximal value 10 or less than all subranges of 10, for example 1 to 6.7, or 3.2 to 8.1, or 5.5 to 10.Equally, in the text the term of Shi Yonging " be deposited on ... on ", " put on ... on " or " ... on provide " mean ... on deposit, apply or provide, but must not contact, for example " be deposited on " material on the substrate and do not get rid of and one or more occur at the material of deposition and other material of the identical or different component between sheet or the substrate with the surface.
Before the non-limiting example of discussing electrode of the present invention, electrochromic cells or glass, be appreciated that, because the present invention can be presented as other embodiment, so the present invention is not limited to shown in the literary composition and the application of the details of the concrete non-limiting example of discussing.In addition, discuss term used in the present invention in the literary composition just for purpose of description rather than determinate.In addition, unless opposite indication is arranged in the following discussion, identical numeral components identical.
In the argumentation below, description of the invention is at the vehicle-mounted electrochromism conversion of single chamber glass.As is understood, the invention is not restricted to this, glass in conjunction with feature of the present invention can have one with upper chamber, for example described glass can have 2,3,4 or multi-cavity chamber more, and can and/or be its parts as the glass of any kind vehicles, the vehicles include but not limited to land craft, as but be not limited to automobile, truck, car, motorcycle and/or train, aircraft and spacecraft, and waterborne and/or underwater vehicle.And, can and/or be its parts as the vehicles glass of any kind (for example, but be not limited to windshield, side window, roof window and rear window) in conjunction with the glass of feature of the present invention.And, can be used as glass pane and/or its parts of residential building, commercial building, oven door, door for microwave oven and refrigerator doors in conjunction with the glass of feature of the present invention.In other non-limiting example of the present invention, electrode of the present invention and/or electrode assemblie can use together with the electrochomeric glass that only has a transparent side and/or be its parts, for example, but be not limited to mirror, such as but not limited to the car scope of the vehicles and the outer side-view mirror of car, and can and/or be its parts as the electrochromic device of any kind.
With reference to Fig. 1 and 2, show the unrestricted embodiment of electrochromic switchable cell of the present invention or glass 20.Glass 20 comprises pair of electrodes assembly 22 and 24, this electrode assemblie 22 and 24 is linked together its internal edge 26 and 28 respectively by spacer element 29, so that the inside surface 30 and 31 of electrode assemblie 22 and 24 separates each other respectively, thereby provide the sealed chamber 32 that holds electrochromism conversion medium 33.In non-limiting example of the present invention, electrode assemblie 22 and 24 inside surface 30 and 31 are separated out respectively and are in the relation that is substantially parallel to each other and faces.This relation is preferred to be realized by spacer element 29.Spacer element 29 can be respectively be positioned between the edge 26 and 28 of electrode assemblie 22 and 24 in the mode of appropriate intervals between any inside surface 30 and 31 that can keep electrode 22 and 24.For example but do not limit the present invention, spacer element 29 forms framework to limit the outer boundary or the boundary line of sealed chamber 32.Spacer element 29 can be made of any material, and is polymeric material in a non-limiting example, for example solidifies organic polymer materials, as thermoplasticity, thermosetting or UV curing resin material.The organic encapsulant of epoxy resin-matrix is especially as spacer element 29, and preformed spacer element can any general mode, and for example (but not limiting the present invention) is adhered to the edge 26 and 28 of electrode assemblie 22 and 24 respectively by moistureproof cohesive sealant (the moisture resistant adhesive sealant) (not shown) of butyl.
In a non-limiting example of the present invention, the chamber 32 with medium 33 is provided with in the following manner.Between the surface of the inward flange 26 of the inside surface 30 of electrode assemblie 22 and polymerization preformed spacing frame element 29, one deck electrical isolation adhesive/sealant (not shown) is set, between the apparent surface of the edge 28 of the inside surface 31 of electrode assemblie 24 and spacing frame element 29, one deck electrical isolation adhesive/sealant (not shown) is set.After bonding coat solidifies or solidifies, with electrochromic media 33 for example by the hole in the spacer element 29 34 (only shown in Figure 2) with arbitrarily easily mode be moved in the chamber 32, then for example by the moistureproof adhesive/sealant (not shown) of butyl with mode seal bore 34 easily arbitrarily, so that electrochromism conversion medium 33 is contained in the chamber 34.The thickness of spacer element 29 preferably equals to be contained in the thickness of the electrochromic media 33 in the spacer element 29, so that electrode assemblie 22 contacts with electrochromic media respectively with 31 with 24 surface 30.
In the electrode assemblie 22 and 24 each comprises sheet or substrate 35 and 36 and electrode 38 and 40 respectively.Each sheet 35 and 36 all has inside surface 42 and outside surface 44, electrode 38 of the present invention is supported on and preferably is fixedly mounted on the inside surface 42 of sheet 35, and electrode of the present invention 40 is supported on and preferably is fixedly mounted on the inside surface 42 of sheet 36.In the argumentation below, the inside surface 30 of electrode assemblie 22 is also referred to as the outside surface 30 of electrode 38, and the inside surface 31 of electrode assemblie 24 is also referred to as the outside surface 31 of electrode 40.
In a non-limiting example of the present invention, as shown in Figure 1, the side 50 of electrode assemblie 22 extends beyond the side 51 of electrode assemblie 24, and the side 52 of electrode assemblie 24 extends beyond the side 53 of electrode assemblie 22, so that be that electrode 38 and 40 provides electrical connection in any common mode.Discussed the non-limiting example of the electrical connection of electrode below.As shown in Figure 2, the side 54 of the sheet 35 of electrode assemblie 22 and 55 or the side 54 of electrode assemblie 22 and 55 usually respectively with the side 56 of the sheet 36 of electrode assemblie 24 and 57 or the side 56 and 57 of electrode assemblie 24 aim at.Other non-limiting example of the present invention comprises respectively, the side 50 and 53~55 of sheet 35, or the electrode assemblie of aiming at the side 51,52,56 and 57 of sheet 36 22, or electrode assemblie 24, and the side 50 and 53~55 of electrode assemblie 22 respectively with the side 51,52,56 of electrode assemblie 24 and 57 skews.
Discuss in more detail as following, the present invention's expectation, " close " when electrochromic cells 20 is in it, when " not variable color " or " bleaching " state, in the electrode assemblie 22 and 24 one or both are to visible transparent, and/or in sheet 35 and 36 one or both be to visible transparent, and/or in electrode 38 and 40 one or both are to visible transparent.This point is appreciated that, when electrochromic cells is used as glass pane or perspective partition plate, two electrode assemblies are all preferably to visible transparent, and when electrochromic cells is used for only through an electrode assemblie and by visible light, for example, electrochomeric glass 20 is as mirror or partition plate with a transparent side surfaces, and it is transparent preferably having only an electrode assemblie.
For purposes of the invention, " to visible transparent " or " transparent " means through the whole visible lights of object, for example but do not limit the present invention, see through an electrode assemblie, or see through an electrode assemblie and electrochromic media, or see through the electrochromic media between two electrode assemblies and two electrode assemblies.Term " visible light " means the electromagnetic radiation with the wavelength in 400~700 nanometer range of electromagnetic spectrum.The invention is not restricted to when this glass is in " closing ", " not variable color " or " bleaching " state, see through an electrode assemblie, or see through an electrode assemblie and electrochromic media, or see through the number percent of the visible light of the electrochromic media between two electrode assemblies of two electrode assemblies and electrochromism conversion glass of the present invention.In a non-limiting example of the present invention, transmission of visible light is greater than 0%, for example, and greater than 30%, or greater than 45%, or greater than 60%.Transmission of visible light is measured according to CIE standard light source A.
The present invention is not limited to the sheet 35 of electrode assemblie 22 and 24 and 36 material respectively, and these sheets can be made by any material, includes but not limited to polymeric material, stupalith, glass ceramic material and glass material.When one in sheet 35 and 36 or both are designated as when having greater than 0% transmission of visible light, sheet can be made by the material to visible transparent, such as but not limited to transparent polymeric material of the present invention, transparent soda-lime-silica glass, transparent Pyrex, or the transparent fireproof glass of any kind, and combination.Be designated as when having 0% transmission of visible light when one or more 35 and 36, sheet can be made by opaque material, can be such as but not limited to metal of the present invention, opaque polymeric material and/or sheet 35 and 36 by having greater than 0% transmission of visible light with on one or two surface of the substrate with 0% transmission of visible light, for example but do not limit the present invention, the lip-deep coating on the surface 42 and/or 44 of sheet 35 or 36 or the substrate of film are made.In the sheet 35 and/or 36 one or two can be the sheet of monolithic, or in these sheets one or two can be two-layer or two-layer above laminate, or the two-layer or two-layer above sheet that is separated by spacing frame, for example but do not limit the present invention, multiple insulation unit, or its combination.
The present invention is not limited to the sheet 35 of electrode assemblie 22 and 24 and 36 peripheral profile, shape and/or thickness respectively. Sheet 35 and 36 sides that can have more than three or three, and these sides can be linearity or nonlinear.Although in practice of the present invention, but the inside surface of sheet 35 and 36 preferably each other equably at interval, so that conversion medium 33 evenly deepening in chamber 32, the surface 42 and 44 of sheet is substantially parallel, minimizing the distortion of being looked object, the present invention expects that in sheet 35 and 36 one or two all has flat surfaces 42 and/or 44; Be parallel to each other or not parallel; Have the surface 42 and/or 44 that is different from flat shape, for example but do not limit the present invention, spill, convex or the wedge shape seen from xsect.Wherein, wedge of glass is disclosed in U.S. Patent No. 5,812, and in 332, this patent is by with reference to being incorporated into this.And the present invention expects that the opposite side of interval from a side of chamber 32 to this chamber between the inside surface 42 of sheet 35 and 36 changes.
As skilled in the art to understand, the present invention does not limit the composition of glass sheet 35 and 36, for example but do not limit the present invention, glass sheet can be colourless (clear) or stained glass, and for example U.S. Patent No. 5,030,592,5,240,886,5,593,929 and 5, disclosed type in 792,559, these patents are incorporated into this by reference.Glass sheet can be annealed glass, chemical tempering or hot tempered glass, or hot-reinforced glass.In a non-limiting example of the present invention, glass is PPG industries, Inc., and Pittsburgh, PA, trade mark is
The chemical tempered glass of II.This glass has extremely high intensity and weight ratio, makes this glass sheet specific heat tempered glass thinner lighter and do not damage intensity and optical.Glass sheet 35 can be identical with 36 composition and/or characteristic, or the composition of sheet and/or characteristic can be different mutually, and for example but do not limit the present invention, a sheet can be a stained glass, and another sheet is a flint glass.In a non-limiting example of the present invention, sheet 35 and 36 is soda-lime-silica glass sheets of clear, colorless.
In addition, one or two in the sheet 35 and/or 36 can have functional coating on outside surface 44.Functional coating includes but not limited to the environment coating, hydrophobic coating and/or dehumidifying or remove the coating of surface contaminant, for example, as the U.S. Patent Application Serial Number submitted on July 23rd, 1997 with people's such as Greenberg name is No.08/899,257 are called disclosed photocatalytic activity automatic cleaning coating in " Photocatalytically-Activated Self-Cleaning Articleand Method of Making Same ", or the U.S. Patent Application Serial Number of submitting on September 2nd, 1997 with the name of James P.Thiel is No.08/927,130 are called in " Photocatalytically-Desiccating Multiple-Glazed Window Units " disclosed light with the electrolysis dry coating, and each application is all by with reference to being incorporated into this.
As illustrated in fig. 1 and 2, electrode 38 and 40 inside surface 30 and 31 respectively mutually in the face of and electrically contact with electrochromism conversion medium 34 in the chamber 32.With reference to Fig. 3, following argumentation is appreciated that unless otherwise indicated that at the electrode 40 of electrode assemblie 24 and electrode assemblie 24 this argumentation is applicable to the electrode 38 of electrode assemblie 22 and electrode assemblie 22.Electrode 40 of the present invention comprises basic unit 60 on the inside surface 42 of sheet 36 and the active layer 62 on the basic unit 60.Term used herein " layer " means one or more layers, or one or more layers film.Active layer 62 has the surface 31 of contact medium 33.Electrode 38 and 40 layer are 60 and 62 in any general mode, for example but do not limit the present invention, apply (being also referred to as " MSVD " here) by chemistry coating, conduction coating, high temperature coating or magnetron sputtering vacuum moulding machine, be deposited on the inside surface 42 of sheet 35 and 36.In preferred practice of the present invention, electrode 38 and 40 layer 60 and 62 deposit by MSVD.
The surface 31 (referring to Fig. 3) of active layer 62 has low sheet resistance, for example but do not limit the present invention, be not more than 20 ohm of every squares, wherein, active layer 62 from chamber 32 outsides by electrode (for example is used to provide, electrode 40) active layer 62 arrives another electrode (for example electrode 38) and passes through the conductive path of the active layer of electrode 38 to the outside of chamber 32 by electrochromic media 33.But the basic unit 60 of electrode 38 and 40 is in the following manner as the anti-sunlight layer zone of heating and/or the electric enhancement layer of active layer 62.
With reference to Fig. 4, in a non-limiting example of the present invention, basic unit 60 is included in ground floor or substrate contact layer 66 thereon on the inside surface 42 of sheet 36, preferred is on the ground floor 66, preferred metal level 68 (being also referred to as " the first metal layer 68 " here) and on metal level 68, preferred bridge layer (bridging layer) 70 thereon thereon.Metal level 68 does not limit the present invention, and can be the material of any suitable formation conductive path and optionally infrared (wavelength is greater than the electromagnetic spectrum of 700 nanometers) reflecting surface.The material that can be used for the present invention practice includes but not limited to silver, gold, copper, aluminium, platinum and alloy thereof, for example but do not limit the present invention, has the alloy of the silver of another kind of metal (making up such as nickel or titanium, gold, copper, platinum, aluminium, silver or its).It should be noted that certain metal film, for example but do not limit the present invention, silverskin has two other resistivity of level and infrared reflectivity.More specifically, when resistivity was in it than low level, infrared reflectivity was in its higher level, and vice versa.In practice of the present invention,, preferably make the resistivity of silverskin be in it for following reason, and infrared reflectivity is in its higher level than low level when infrared reflecting layer (being also referred to as " IR " here) when being silverskin.
In a non-limiting example of the present invention, the more low-level resistivity of metal level 68 and the infrared reflectivity of higher level are to realize by the ground floor 66 with some particular characteristics.In a non-limiting example of the present invention, these characteristics include the atomic arrangement of the deposition that helps low resistance, high reflectance, metal level 68, and chemistry and thermal stability.Usually, a skim does not have whole above-mentioned particular characteristics; Therefore, in a non-limiting example of the present invention, ground floor 66 has two-layer or multilayer film, for example but do not limit the present invention, ground floor 66 is U.S. Patent No.s 5,821, disclosed type in 001, its disclosure is incorporated into this by reference, to improve low resistance, the high reflectance characteristic of metal level 68.More specifically, but do not limit the present invention, ground floor 66 comprises the metal contact layer 72 that contacts with metal level 68, and between the sheet 35 of metal contact layer 72 and electrode assemblie 22, and supporting layer 74 between the sheet 36 of metal contact layer 72 and electrode assemblie 24.The material of metal contact layer 72 has crystallization property so that the atom that forms metal level 68 with in two resistivity ranks than higher level deposition in low level and two the infrared reflectivity ranks.The metal contact layer 72 of the ground floor 66 of basic unit 60 is selected with the ability of the form deposition of low-resistivity rank and high infrared reflection rate level characteristics according to the atom that makes metal level 68.Metal level 68 and metal contact layer 72 cooperatively interact, and this means that the low-resistivity rank of metal level 68 is relevant with the special architectural feature of the metal contact layer 72 of ground floor 66 with high infrared reflection rate rank.For example, the crystal structure of metal level 68 can represent the orientation relationship with metal contact layer 72, and this causes the bigger crystal grain in the metal level 68 conversely, or in other words, less zone, grain boundary, or other less electron scattering defective.
Generally speaking, the material of selecting to be used for metal contact layer 72 will depend on the homogeneity of metal level.In non-limiting example of the present invention, metal level 68 is silverskin 68.Preferred silverskin is because of its economy and is easy to by MSVD deposition and reflective infrared energy.At metal level 68 is under the situation of silverskin, and the example of suitable material of metal contact layer 72 that is used for the ground floor 66 of basic unit 60 is Zinc oxide films.In the deposition process of Zinc oxide film, note selecting technological parameter, described technological parameter provide suitable crystallinity for Zinc oxide film or the crystal growth of selecting the superior orientation so that advantageously influence the deposition of silver atoms, and described technological parameter changes low-resistivity, the high reflectance characteristic that has promoted silverskin.A kind of mode of doing like this is to make oxygen surpass argon during the sputter of casting zinc metallic target.Other suitable material that is used for the metal contact layer 72 of ground floor 66 includes but not limited to, from the zinc oxide aluminum and the tin indium oxide of the ceramic tile sputter of suitable composition.
Supporting layer 74 support metal contact layers 72, and comprise one or more layers film.In a non-limiting example of the present invention, supporting layer 74 comprises that one deck has chemical resistance and stable on heating film at least.The suitable material that is used for supporting layer includes but not limited to, the amorphous sputter oxide (being also referred to as " zinc stannate " here) of zinc and tin and the amorphous oxide of tin or bismuth.For high-transmission rate and low-launch-rate application, the film of supporting layer 74 preferably not absorbing in the visible and infrared part of electromagnetic spectrum.In non-limiting example of the present invention, supporting layer 74 is zinc stannate films, because it is glued fast to the inside surface 42 of glass sheet 35 and 36 very much, also because its better chemical stability (zinc stannate is not easy to be subjected to acid or end liquid corrodes) and thermal stability (zinc stannate can be heated to and not deterioration) to 1200 °F.The more detailed argumentation of zinc stannate characteristic is disclosed in U.S. Patent No. 4,610,771, and its disclosure is incorporated into this by reference.
The present invention does not limit the percentage by weight of tin and zinc in the zinc stannate film; More particularly, the zinc stannate film can have the tin of 10~90% weight and the zinc of 90~10% weight; The zinc of the tin of 10~40% weight and 60~90% weight; The zinc of the tin of 34% weight and 66% weight; The zinc of the tin of 53% weight and 47% weight; Or the zinc of the tin of 48% weight and 52% weight.
Because only the atom in the deposition of the atom pair metal level 68 of the near surface of metal contact layer 72 works, usually, the thickness of metal contact layer should be minimised as the acquisition expectation to be reduced the resistance of metal level 68 (silver layer 68 for example recited above) and increases the needed thickness of infrared reflectivity, thereby can maximize the thickness of chemical more and heat-staple supporting layer 74.Be described below the film thickness scope that is used for ground floor 66.
As understandable, the present invention does not limit the quantity that is included in the film in the ground floor 66, and ground floor 66 can have greater or less than two membranes, for example, has only one deck Zinc oxide film or have only one deck zinc stannate film between metal level 68 and sheet 35 and/or 36.And the present invention does not limit the composition of the film of ground floor 66, and ground floor can use any film, for example the dielectric film that uses between metal film and substrate (for example plastics or glass sheet) in the prior art.
As skilled in the art to understand, do not form well when bonding with surface 42 when the surface of the ground floor 66 that contacts with surface 42 separately in the sheet 35 and 36 in these examples, prime coat (primer layer) (not shown) can be used for ground floor 66 with electrode 38 and/or 40 and be fixed to its sheet 35 or surface 42 of 36 separately.For example, but do not limit the present invention, be called disclosed prime coat type in " A Vision Panel Having a Multi-layer Primer " in U.S. Patent Application Serial Number for the No.___ name, can be when sheet 35 and/or 36 is plastic sheet for example the ground floor 66 of electrode 38 and/or 40 be fixed to it separately on plastic sheet 35 or 36 the surface 42.
The part order of the ground floor 66 of the basic unit 60 on the non-limiting example imagination sheet of the present invention is to include but not limited to: sheet 35 or 36/ ground floor, 66/ metal level 68; Sheet/metal supporting layer 74/ metal contact layer 72/ metal level 68; Glass sheet/dielectric layer/metal level; Glass sheet/first dielectric film/second dielectric film/metal film, and glass sheet/zinc stannate film/Zinc oxide film/silverskin.
The bridge layer 70 of basic unit 60 is deposited on the first metal layer 68 of basic unit 60.Bridge layer 70 of the present invention has different functions according to the desired structure of electrode 38 and/or 40 with operation.In order to fully understand bridge layer 70, present argumentation then, is discussed at bridge layer 70 at active layer 62.
As skilled in the art to understand, metal is the fabulous conductor of electric current, but not all metal (for example, silver and metal alloy) all with electrochromic switchable cell in the electrochromic media compatibility used.Also as skilled in the art to understand, most of metal oxides than metal more with electrochromic switchable cell in the electrochromic media compatibility used.But, good not as metal as the most of metal oxides of the conductor of electric current.According to noted earlier, in a non-limiting example of the present invention (referring to Fig. 4), active layer 62 is included in the conductive metal oxide layer 80 on the metal level 78 (below be called " second metal level 78 ").In order to prevent the oxidation of second metal level 78 in the sputter procedure of conductive metal oxide layer 80; as known in the art; before metal oxide layer 80 being splashed on second metal level 78, on second metal level 78, apply protective seam or sacrifice layer 82.
The material that can be used for second metal level 78 in practice of the present invention comprises the above-mentioned material that can be used for the first metal layer 68.The present invention does not limit the material of metal oxide layer 80, but selected materials should be conduction and should with electrochromic media 33 compatibilities, for example but do not limit the present invention, should not weaken or damage the conversion characteristics of medium.The metal oxide layer 80 that is used for transparency electrode should be transparent, and is antireflecting in a non-limiting example.The material of the metal oxide layer 80 that can be used for conducting electricity in practice of the present invention includes but not limited to the material selected from the group of the nitride of the oxynitride of conducting metal oxide, metal alloy, conduction and conduction.In another non-limiting example of the present invention, layer 80 is to cause the metal oxide that conducts electricity by doping, and it includes but not limited to mix tin-oxide, the halogen that especially mixes (for example, fluorine (SnO
2: F)) or antimony dopant (SnO
2: tin oxide Sb), or the zinc paste of mix aluminium (ZnO:Al) for example or doped tin (ZnO:Sn) or doped with fluorine (ZnO:F) or doped indium (ZnO:In); The indium oxide of doped tin (ITO); The zinc stannate of conduction; The stannic acid cadmium; The tin oxide of doped indium, and combination.In another non-limiting example of the present invention, conductive metal oxide layer 80 is indium tin oxide layer or zinc paste aluminium lamination.In preferred practice of the present invention, but the present invention is not restricted to this, and conductive metal oxide layer 80 is indium tin oxide layers.
The material that can be used for protective seam 82 in the present invention's practice comprises metal, such as but not limited to, zirconium, titanium, copper metal oxide and metal nitride, such as but not limited to, non-stoichiometric tin indium oxide and titanium nitride.More specifically, non-stoichiometric tin indium oxide is to obtain by sputter tin indium oxide negative electrode in inert atmosphere (for example, but be not limited to 100% argon gas).On the other hand, stoichiometric tin indium oxide is to obtain by sputter tin indium oxide negative electrode in reactive atmosphere (for example, but being not limited to 5% oxygen, 95% argon gas).In non-limiting example of the present invention; the protective seam 82 negative electrode target by sputter material in nonactive atmosphere (for example; sputter copper target in argon atmosphere) is applied on second metal level 78; with negative electrode target (for example, sputter tin indium oxide target in reactive atmosphere) sputter second metal oxide layer 80 on protective seam 82 by sputter different materials in reactive atmosphere.In another non-limiting example of the present invention; protective seam by sputter ceramic cathode target in nonactive atmosphere (for example; sputter tin indium oxide negative electrode target in argon atmosphere) be deposited on second metal level 78 with deposition protective seam 82, and after this in reactive atmosphere sputter indium negative electrode target with depositing metal oxide layer 80.As is understood; the invention is not restricted to sputter tin indium oxide negative electrode target in inert atmosphere; afterwards in reactive atmosphere this target of sputter so that protective seam 82 and conductive metal oxide layer 80 to be provided; other stupalith also can be used for practice of the present invention; such as, but not limited to U.S. Patent No. 6; 398; disclosed stupalith in 925, it includes but not limited to conduct electricity the tin oxide, stannic acid cadmium, the tin oxide of doped with fluorine, the tin oxide of doped indium, the indium oxide of doped tin, the zinc paste and the combination thereof of doped indium of zinc stannate, antimony dopant.
The non-limiting example of active layer 62 of the present invention includes but not limited to, metal level (78)/protective seam (82)/conductive metal oxide layer (80); Metal level/deposition is as the protective seam/conductive metal oxide layer of metal level; Copper film/the indium oxide tin film of silverskin/in inert atmosphere, deposit, the indium oxide tin film of the indium oxide tin film of and silverskin/in inert atmosphere, deposit/in reactive atmosphere, deposit.
Continuation is with reference to Fig. 4, and present argumentation is at the bridge layer 70 of the basic unit 60 of electrode 38 and 40 (only showing electrode 40 among Fig. 4).As mentioned above, also be suitable for electrode 38 at the argumentation of electrode 40, unless otherwise noted.Bridge layer 70 is included in protection or sacrifice layer 88 and the articulamentum 90 between active layer 62 and protective seam 88 on the first metal layer 68.The argumentation of above-mentioned protective seam 82 about active layer 62 also is suitable for the protective seam 88 of bridge layer 70, unless otherwise noted.
The articulamentum 90 of bridge layer 70 physically separates the first metal layer 68 of basic unit 60 and second metal level 78 of active layer 62, so that two conductive layers and optional two infrared reflecting layers to be provided to electrode 40.Two infrared reflecting layers for example are respectively first and second metal levels 68 and 78, have reduced the number percent of infrared energy transmissivity (for example, by the electromagnetic spectrum wavelength more than 700 nanometers of electrode assemblie 22 and/or 24).This minimizing of infrared energy transmissivity can reduce the adverse effect of infrared energy to electrochromic media 33, and can reduce thermal loss by electrochomeric glass 20, for example, by this unit from vehicle interior to the migration heat of outside cold environment and by this unit from the external environment condition of sweltering heat heat to nice and cool vehicle interior migration.
In a non-limiting example of the present invention, the articulamentum 90 of the bridge layer 70 of basic unit 60 is conduction articulamentum 90A, to provide conductive path to electrode, this conductive path comprises the first metal layer 68 of basic unit 60, the conduction articulamentum 90A of basic unit 60 and active layer 62.Term " conduction articulamentum " means that articulamentum 90A has the feasible electric current at least 50% that is applied to the first metal layer 68 of basic unit 60 of resistance, for example 75~100% or 90~100%, arrive second metal level 78 of active layer 62 by articulamentum 90A, thereby increase, promptly enhanced flow is crossed the levels of current of second metal level 78.For example, if 2 amperes electric current is applied to the first metal layer 68 of layer 60, and 60% electric current that is applied to the first metal layer 68 arrives second metal level 78 of active layer 62 by articulamentum 90A, the second layer 78 will receive 60% the electric current that applies, or 1.2 amperes, the first metal layer 68 will have 40% the electric current that applies, or 0.8 ampere.In conjunction with metal level 68 and 78, effectively increased the thickness of electrode conducting path, this has shortening electrochromic media is transformed into the influence of the time of low visible light transmissivity from high visible light transmissivity, as mentioned above.
In a non-limiting example of the present invention, conduction articulamentum 90A is one or more above-mentioned conductive metal oxide layers.In another non-limiting example of the present invention, articulamentum 90A is the zinc stannate film of indium oxide tin film or conduction.Still in another non-limiting example of the present invention, the metal level 78 of active layer 62 is the silverskin on the articulamentum 90A, and conduction articulamentum 90A comprises the support membrane 94A of the conduction zinc stannate layer on the protective seam 88 and the Metal Contact film 72 on the layer 94A.As skilled in the art to understand; protective seam 82 and 88; they are nonconducting with regard to the metal supporting layer 72 of articulamentum 90A; it is minimum that the effect of the resistance that electric current is flowed is considered to; because the thickness of expectation is little; for example in a non-limiting example of the present invention, protective seam 82 and 88 is to have the copper film of thickness less than 25 dusts, and the metal supporting layer 72 of articulamentum 90A is thickness Zinc oxide films in 50~80 dust scopes.
In another non-limiting example of the present invention, articulamentum 90 the flowing that be high resistance articulamentum 90B with second metal level 78 of restriction electric current from the first metal layer 68 of basic unit 60 to active layer 62.Term " high resistance articulamentum " means that articulamentum 90B than an electrode (for example has, electrode 40) active layer 62 and another electrode are (for example, electrode 38) the big resistance of resistance between the active layer 62, thereby be applied to electrode basic unit 60 the first metal layer 68 less than 50%, for example 0~25% or 0~10% electric current arrives second metal level 78 of active layer 62 by articulamentum 90B.In a non-limiting example of the present invention, articulamentum 90B is the dielectric layer type that is used for low radiation sputter-coated glasses technology.In another non-limiting example of the present invention, articulamentum 90B comprises dielectric layer 94B, for example the alumina silicate film.In another non-limiting example of the present invention, second metal level 78 is the silverskin on the articulamentum 90B, and articulamentum 90B comprises dielectric layer 94B; for example, dielectric zinc stannate film on the protective seam 88 and Metal Contact film 72; for example, the Zinc oxide film on the dielectric layer 94B.
To be heated to remove the mist on the outside surface at outside surface 44 when sheet 35 and 36, and/or heating electrochromic media 33 is so that under the situation under cold snap during faster conversion, electric current is by each the first metal layer 68 of basic unit 60 in the electrode 38 and 40, with heating plate 35 and 36 and/or electrochromic media.Wanting under the reformed situation when the transmission of visible light of electrochromism conversion medium 33, () active layer 62 for example, electrode 40 arrives the active layer 62 of another electrodes (for example, electrode 38) to electric current by electrochromic media 33 by an electrode.As now understandable, high resistance articulamentum 90B prevents or the metal level 78 of the current direction active layer 62 of the first metal layer 68 of restricted passage basic unit 60 or from its outflow.Such as will be appreciated, the invention is not restricted to use and be used for filming of high resistance articulamentum 90B, and the present invention's expectation provides electrical insulation sheet, for example but do not limit the present invention, a plastic layer, for example but do not limit the windshield that is used to make lamination and be fixed on the first metal layer 68 or the protective seam 88 and active layer 62 is coated to interlayer plastic sheet type on the interlayer sheet; By E.I.Du Pont de Nemours andCompany; Delaware sells; registered trademark is the polyester film of the type of MYLAR; have active layer 62 that on one side, applies and the first metal layer 68 or the protective seam 88 that adheres to opposite face; or the plastic liquid rete that solidifies that is applied on metal tunic 68 or the protective seam 88, solidifies; for example liquid acrylic film, and active layer 62 is applied on the acrylic film of curing (referring to Fig. 4).Use above-mentioned technology, when the transmission of visible light of electrochromism media changes, glass sheet 35 and 36 and/or media 33 can be heated.Thereby bus-bar can be connected to electrode and and one or more power supply can be connected to bus-bar and realize aforementioned content with any usual manner (for example, following mode described below) that makes things convenient for, and these bus-bars, power supply and electrical connection do not limit the present invention.
The non-limiting embodiment of the articulamentum 70 on the first metal layer 68 of the basic unit 60 of the electrode of the present invention 38 with conduction articulamentum 90A and/or 40 includes, but not limited to the first metal layer 68/ conductive metal oxide layer; The first metal layer 68/ protective seam 88/ tin indium oxide; Protective seam/the tin indium oxide of the first metal layer 68/ tin indium oxide and the first silver metal layer 68/ are deposited on copper film on the silver layer/the be deposited on indium oxide tin film on the copper film.The non-limiting embodiment of the articulamentum 70 on the first metal layer 68 of the basic unit 60 of the electrode of the present invention 38 with high resistance articulamentum 90B and/or 40 includes, but not limited to the first metal layer 68/ sheet of insulation, for example, and plastic sheet; The first metal layer 68/ dielectric layer; The first metal layer 68/ protective seam 88/ thick Zinc oxide film, for example, at least 100 dusts; The dielectric layer of the first metal layer 68/ protective seam/zinc stannate and the first silver metal layer 68/ are deposited on copper film on the silver layer/be deposited on the dielectric layer of the zinc stannate on the copper film and are deposited on Zinc oxide film on the zinc stannate film.
Shown in Fig. 5 is the non-limiting example of electrochromism conversion glass 100 of the present invention, it can be used to make electric current to flow through electrode 38 and 40 and electrochromic media 33, so that medium 33 deepenings, and/or make excess current flow through electrode 38 and 40 outside surface 44 and electrochromic medias 33 with heating plate 35 and 36.Electrochromism conversion glass 100 is similar with the electrochromism conversion glass 20 shown in Fig. 1 and Fig. 2, and its difference is described below.(referring to Fig. 2 and Fig. 5) aimed at its side 51,52,56,57 certainly of sheet 36 in the side 50 of sheet 35 and 53~55.The side 54 and 55 of spacer element 29 and sheet 35, the side 56 of sheet 36 and 57 is aimed at, as shown in Figure 2.Spacer element 29 lays respectively at the side 50 of sheet 35 and 36 and 51 inboard, as shown in Figure 5, first outside 104 with first outside 102 and electrode 40 that electrode 38 is provided, and spacer element 29 lays respectively at the side 53 of sheet 35 and 36 and 52 inboard, with second outside 108 of second outside 106 and electrode 40 that electrode 38 is provided.Each has bus-bar 110 and 112 respectively second outside 108 (referring to Fig. 5) of first outside 102 of electrode 38 (referring to Fig. 5 and Fig. 5 A) and electrode 40, and it distinguishes the first metal layer 68 of the basic unit 60 of contact electrode 38 and 40, the bus-bar 110 shown in Fig. 5 A.Each has bus-bar 114 and 116 respectively first outside 104 (referring to Fig. 5) of second outside 106 of electrode 38 (referring to Fig. 5 and Fig. 5 B) and electrode 40, it contacts the first metal layer 68 of basic unit 60 and the active layer 62 of electrode 38 and 40, the bus-bar 114 shown in Fig. 5 B respectively.
With reference to Fig. 6, in a non-limiting example of the present invention, bus-bar 116 and 110 is connected to the positive terminal of direct supply 120 respectively by distribution 122 and 123, and bus-bar 112 and 114 is connected to the negative terminal of power supply respectively by distribution 124 and 125.Switch 127 and 128 be separately positioned on bus-bar 110 and 116 and the positive terminal of power supply 120 between, and switch 129 and 130 be separately positioned on bus-bar 112 and 114 and the negative terminal of power supply 120 between so that make its separately bus-bar be electrically connected with power supply 120 or disconnect.More specifically, be shown in an open position and switch 128 and 130 is in the close position by switch 127 and 129, electric current between bus-bar 116 and 114, electrode 38 and 40 active layer 62 flow, and flow through electrochromic media 33 to change the transmission of visible light of electrochromic media.Be shown in an open position by switch 127 and 130, switch 128 and 129 is in the close position, electric current between bus-bar 116 and 112, flow and the metal level 68 that flows through electrode 40 with heating plate 36 and electrochromic media 33.Be shown in an open position by switch 128 and 129, switch 127 and 130 is in the close position, and electric current flows between bus-bar 110 and 114, and the metal level 68 by electrode 38 is with heating plate 35 and electrochromic media 33.Be in the close position by switch 127~130, electric current flows between bus-bar 110,112,114 and 116, the metal level 68 that flows through electrode 38 and 40 is with heating plate 35 and 36 and electrochromic media, and electric current flows through the active layer 62 of electrode 38 and 40 and electrochromic media 33 to change the transmission of visible light of electrochromic media.In a non-limiting example of the present invention, variohm 132 be arranged on bus-bar 110 and 116 and positive terminal between, and variable resistor 132 be arranged on bus-bar 112 and 114 and the negative terminal of power supply 120 between, by electrode 38 and 40 the metal level 68 and the flow of active layer 62, making has enough electric currents to flow through the speed of medium 33 with the expectation of the change of the transmission of visible light aspect that is implemented in medium 33 with Control current.Because foregoing circuit is simple relatively to those skilled in the art, so do not need this circuit is described further.
With reference to Fig. 7, show another non-limiting example of the present invention, comprise electrochromism conversion glass 140, it transmits different voltage, and for example the voltage by the first metal layer 68 is higher than the voltage by the active layer 62 of electrode 38 and 40.Glass 140 comprises the bus-bar 142 of the first metal layer 68 1 sides that are connected to electrode 38, is connected to the bus-bar 144 of the first metal layer 68 opposite sides of electrode 38; Be connected to electrode 40 the first metal layer 68 a side bus-bar 146 and be connected to the bus-bar 148 of the first metal layer 68 opposite sides of this electrode 40; Be connected to electrode 38 active layer 62 one or more sides bus-bar 150 and be connected to the bus-bar 152 of one or more sides of the active layer 62 of electrode 40.With reference to Fig. 7 A, bus-bar 144 and 148 is connected to positive terminal by distribution 154 and 155 respectively, and bus-bar 142 and 146 is connected to the negative terminal of direct supply 160 respectively by distribution 156 and 157.Alternatively, switch 162 is arranged between the positive terminal of bus-bar 144 and power supply 160, and switch 163 is arranged between the positive terminal of bus-bar 148 and power supply 160, optionally to make electric current pass through its electrode 38 separately and 40 the first metal layer 68, with heating plate 35 respectively and 36 and electrochromic media 33.
Continuation is with reference to Fig. 7 A, and bus-bar 150 is by the positive terminal of distribution 165 connection direct supplys 164, and bus-bar 152 connects the negative terminal of direct supplys 164 by distribution 166.Alternatively, thus switch 168 is arranged between bus-bar 150 and the power supply 164 optionally to make electric current pass through the transmission of visible light that active layer 62 changes media 33.The voltage of power supply 120 (Fig. 6) and 160 and 164 (referring to Fig. 7 A) is not limited to the present invention.The voltage at medium 33 two ends should enough highly not damage medium 33 with the transmission of visible light that changes medium.More specifically, have recognized that the voltage that is higher than 1.5 volts can cause any moisture and/or the moisture electrolysis that exists in the conversion medium 33, this meeting permanent damage conversion medium, and not conversion again of medium 33.Although do not limit the present invention, be not more than 5 volts voltage usually, for example be not more than 2 volts, or be not more than 1.5 volts, or be not more than 1.2 volts voltage, for example but do not limit the present invention, be applied to electrode 38 and 40 two ends by the active layer 62 of electrode 38 and 40 with by medium 33.
But the first metal layer 68 by electrode 38 and 40 with heating plate 35 and 36 and the voltage of medium 33 preferably with the coating that is applied to heated windshield on voltage similar, for example in U.S. Patent No. 6, disclosed such in 561,460, this patented claim is incorporated into this by reference.Non-limiting example of the present invention comprises power supply 160, and it has the output of 40 volts, 20 volts, 14 volts or 12 volts.
In the practice of the non-limiting example of the present invention shown in Fig. 7 and Fig. 7 A, be shown in an open position with switch 162 by switch 163 and 168 and be in the close position, electric current flows through the metal level 68 of electrode 38 with heating plate 36 and electrochromic media 33; Be shown in an open position with switch 163 by switch 162 and 168 and be in the close position, electric current flows through the metal level 68 of electrode 40 with heating plate 36 and electrochromic media 33, and be shown in an open position with switch 168 by switch 162 and 163 and be in the close position, electric current flows through the active layer 62 of electrode 38 and 40 to change the transmission of visible light of electrochromic media 33.The present invention expects above-mentioned various combination.
With reference to Fig. 7 and Fig. 7 B, show another non-limiting example of the present invention, has respectively the bus-bar 142,146 and 152 and be connected to the bus-bar 144,148 and 150 of positive source terminal respectively by distribution 154,155 and 165 that is connected to power supply 160 negative terminals by distribution 156,157 and 166.Switch 162,163 and 168 is separately positioned between the positive terminal of bus-bar 144,148,150 and power supply 160.A kind of variable voltage output configuration 170 that progressively reduces voltage type that this area is commonly used is arranged between the positive terminal of bus-bar 150 and power supply 160, thereby prevents to damage medium 33 with the voltage that reduces alternatively between bus- bar 150 and 152.
Such as will be appreciated, the invention is not restricted to the circuit design that any special conductive layer for electrode is powered, any electric current that makes well known in the art all can be used for practice of the present invention by the circuit of the electrode of electrochomeric glass or unit.
Such as will be understood by the skilled person in the art, each electrode 38 all can have identical layer and/or film or different layer and/or films with 40 basic unit 60 and/or active layer 62.For example, in a non-limiting example of the present invention, the outside surface 44 of a sheet (for example sheet 35) of one of electrode assemblie is towards the inside (not shown) of the vehicles, and electrode has basic unit 60 and the active layer 62 that has resistive formation 90B, and (for example, sheet 36) outside surface 44 is towards the outside of the vehicles, and electrode has the basic unit 60 that has conduction articulamentum 90A for the sheet of another of electrode assemblie, for example, indium oxide tin film.By this way, has metal level 68 towards the electrode assemblie of vehicle interior as zone of heating, and the electrode assemblie towards vehicles outside has metal level 68, and it promotes electric current to flow from the superposed metal layer 78 of metal level 68 to active layer 62, as mentioned above.In another non-limiting enforcement side example of the present invention, electrode 38 and/or 40 can only comprise the basic unit 60 with conduction articulamentum 90A.For example but do not limit the present invention, electrode assemblie can include but not limited to sheet/first dielectric layer 66 (for example, zinc stannate film and Zinc oxide film)/metal level 68 (for example, silverskin)/protective seam 88/ conduction articulamentum 90A (for example, indium oxide tin film).And electrode 38 and 40 layer 60 and 62 can be made of identical or different material.And the thickness of electrode can identical or mutual difference.
In an embodiment of the present invention, comprise the electrode with two metal levels, one is used to provide heat, and another is used to operate electrochromic cells, when setting layer thickness between metal level, should consider to be arranged on the voltage between two metal levels.More specifically, it has been recognized that too high if the voltage between the metal level becomes, then the dielectric layer between the metal level may destroy, thereby cause the insulating property forfeiture between the metal level.As a result, when the material of selecting the dielectric layer between the metal level and/or thickness, consider the magnitude of current and the voltage that is set in therebetween in each metal level.Be to be understood that when film was used for dielectric layer, this concerned particular importance.
The present invention does not limit the thickness of electrode layer, and the thickness of these layers should be selected so that the electrochromic cells with at least one transparency electrode assembly 22 and/or 24 to be provided.And, such as will be appreciated, the invention is not restricted to the material of above-mentioned layer and film, and any well known in the art filming may be used in the practice of layer 66,80 and 90 the non-limiting example among the present invention, such as but not limited to tin indium oxide, zinc stannate, zinc paste, tin oxide, silicon dioxide, silicon nitride, silicon oxynitride and potpourri and combination thereof.
The basic unit 60 of electrode and the layer thickness of active layer 62 do not limit the present invention, and when preferably selecting not to be applied in voltage with active layer 62 when electrode to electrochromism conversion glass of the present invention provide greater than 0% transmission of visible light and in a unrestricted embodiment greater than 50% transmission of visible light, with the surface that electrode is provided, for example, to be lower than the layer resistivity of 20.0 ohm of every squares, for example but do not limit the present invention, layer resistivity less than 10 ohm of every squares, for example, less than 5 ohm of every squares or be not more than the layer resistivity of 3.5 ohm of every squares, the electrode 38 of contact electrochromism conversion medium 33 and 40 surface 30 and 32 (referring to Fig. 1 and Fig. 2).In another non-limiting example of the present invention, the thickness of the basic unit 60 of selection electrode and the layer of active layer 62 and index provide muted color to glass or unit 20, and/or provide transmitted colors to glass with when electrode does not apply voltage.
With reference to Fig. 4, about basic unit 60 and do not limit the present invention, when ground floor 66 was dielectric layer, ground floor had in 100~800 dust scopes, for example in the scope of 200~400 dusts, or the thickness in the scope of 250~350 dusts.When the supporting layer 74 of ground floor 66 is that zinc stannate film and Metal Contact film 72 are when being Zinc oxide film, the zinc stannate film has in 50~320 dust scopes, for example in 120~320 dust scopes or the thickness in 150~250 dust scopes, and Zinc oxide film has in 50~300 dust scopes, for example the thickness that 80~200 dust scopes are interior or 100~200 dust scopes are interior.The first metal layer 68 has in 80~300 dust scopes, for example the thickness that 120~250 dust scopes are interior or 130~250 dust scopes are interior.When the first metal layer 68 was silverskin, silverskin had in 80~300 dust scopes, for example the thickness that 90~200 dust scopes are interior or 90~150 dust scopes are interior.When articulamentum 90 was high resistance articulamentum 90B, this layer had in 150~1000 dust scopes, for example the thickness that 400~800 dust scopes are interior or 450~700 dust scopes are interior.When articulamentum 90B comprises zinc stannate dielectric film and Zinc oxide film, the zinc stannate dielectric film has in 200~700 dust scopes, for example in 220~500 dust scopes or the thickness in 250~350 dust scopes, and Zinc oxide film has in 50~300 dust scopes, for example the thickness that 80~200 dust scopes are interior or 100~200 dust scopes are interior.When articulamentum 90 was conduction articulamentum 90A, this layer had in 50~750 dust scopes, for example the thickness that 80~600 dust scopes are interior or 100~400 dust scopes are interior.When contact layer 90A was indium oxide tin film, this film had in 50~600 dust scopes, for example the thickness that 100~500 dust scopes are interior or 250~400 dust scopes are interior.
About active layer 62 and do not limit the present invention, second metal level 78 can have in 80~300 dust scopes, for example in 120~250 dust scopes or the thickness in 130~250 dust scopes.When metal level 68 was silverskin, silverskin can have in 80~300 dust scopes, for example the thickness that 120~250 dust scopes are interior or 130~250 dust scopes are interior.Conductive metal oxide layer 80 can have in 50~750 dust scopes, for example the thickness that 80~600 dust scopes are interior or 100~400 dust scopes are interior.When conductive layer 80 was indium oxide tin film, this film can have in 50~600 dust scopes, for example the thickness that 100~500 dust scopes are interior or 250~400 dust scopes are interior.
Whether the protective seam 82 of active layer 62 and basic unit 60 and 88 optional thickness will want heat-treated to change according to electrode assemblie 22 of the present invention and 24 in the process of making electrode assemblie respectively.Because the basic role of protective seam 82 and 88 is to protect metal level respectively; silverskin 78 and 68 for example; oxidation when preventing on its metal level separately depositing conducting layer 80 and contact layer 90 is not so this protective seam can approach when not accepting thermal treatment in the manufacture process of electrode assemblie of the present invention at electrode assemblie." approaching " used herein is meant that each protective seam all has the thickness of 8 to the 12 dust orders of magnitude.Because the oxidation that thermal treatment is normally strong especially, thus the thickness of protective seam can be increased to, for example but do not limit the present invention, the metal level of the thickness of 20 dusts below protection in the heating process of electrode assemblie.
Although do not limit the present invention, electrode 38 and 40 each all have in 500~3000 dust scopes, for example in 950~3000 dust scopes or the thickness in 950~2000 dust scopes.And, in a non-limiting example of the present invention, select the gross thickness of electrode to think that final outward appearance provides suitable anti-reflection effect, color for example is for example in U.S. Patent No. 4,610,771; 5,821,001; Disclosed product in 6,833,194 and 6,899,953, for example transparent electrochromic cells and/or electrode assemblie.These disclosures are incorporated into this by reference.Because known in the art to being chosen in of dielectric metal oxide, conducting metal oxide and/or the metal layer thickness of sputtering sedimentation and index, need not to further describe for obtaining desired color and transmittance percentage.
As mentioned above, silverskin is degenerated infrared energy (below be also referred to as " IR ") from the IR that chamber 34 reflects to prevent conversion medium 33.In another non-limiting example of the present invention, by U.S. Patent No. 5,240,886 and 5,593,929 cerium oxide and/or the titanium dioxide of discussing can provide these sheets, to absorb ultraviolet energy, for example wavelength coverage is degenerated with the UV that prevents conversion medium 33 less than the electromagnetic spectrum of 400 dusts (below be also referred to as " UV "), and these patents are by with reference to being incorporated into this.In another non-limiting example of the present invention, as known in the art, glass is formed the adjuvant that can comprise absorbing IR, and sheet can be coated with reflection UV radiation.
Electrochomeric glass or unit 20 (as 1 and Fig. 2), 100 (Fig. 5) and/or 140 (Fig. 7) can have arbitrary dimension and shape, and this size and dimension can be selected according to the special intended use of glass 20.For example but do not limit the present invention, electrochomeric glass 20 can have the geometric configuration of symmetry; More specifically, glass 20 can be square or rectangle.This symmetric shape glass is particularly useful for the building glass window, such as, but not limited to window or window assembly.And the present invention imagines unit 20 and has asymmetrical geometric configuration; More specifically, the sheet 35 of glass and 36 can have nonlinear side and/or sheet 35 and 36 can have curved exterior surface 44, and/or curved inner surface 42.The glass of this asymmetrical shape is particularly useful for but is not limited to vehicles glass, such as but not limited to windshield, side window, rear window and roof window.
In the non-limiting example of the invention described above, when by bus-bar 150 and 152 to electrode (example is electrode 38 and 40 as shown in Figure 7) when applying voltage, the transmission of visible light of the electrochromic media 33 in the chamber 34 reduces, and sheet 35 and 36 passes through bus-bar 142 and 144 and 146 and 148 heating electrodes when applying voltage, as mentioned above.But, the invention is not restricted to the design of this bus-bar, and the design of any bus-bar may be used in the practice of the present invention so that bus-bar is connected with metal layer of electrodes with arrangement.For example but do not limit the present invention, as U.S. Patent No. 6,064,509 and 6,471,360 neutralizations are No.____ with its U.S. Patent Application Serial Number of submitting to simultaneously, and name is called the arrangement of disclosed bus-bar and bus-bar in " An ElectrochromicVision Panel Having a Plurality of Connectors ", can be used in the practice of the present invention.And but do not limit the present invention, bus-bar can be the conductivity ceramics base mud type of using in the automotive field, it is fired on the inside surface 42 of sheet 35 and 36, and electrode can be coated on the ceramic bus-bar.Further, such as will be appreciated, the size and dimension of bus-bar does not limit the present invention, and can be suitable for the special geometry of electrochomeric glass.
The voltage level that is applied to conversion medium 33 does not limit the present invention; But, such as will be understood by the skilled person in the art, apply too high voltage and can damage medium 33.More specifically, recognize that the voltage that is higher than 10 volts can cause any moisture and/or the wet steam electrolysis that exists in the conversion medium 33, this meeting permanent damage conversion medium, and not conversion again of medium 33.Although do not limit the present invention, the voltage that is applied to usually on the medium 33 is not more than 5 volts, for example is not more than 2 volts, or is not more than 1.5 volts, or be not more than 1.2 volts.Such as will be appreciated, under the situation of medium 33 moisture-frees and wet steam, can use high level voltage.
Between electrode and the electrochromism conversion medium 33 that is in contact with it does not limit the present invention, and any known media type all can be used for practice of the present invention in this area, for example, electrochromic solutions, electrochromism gel, electrochromism semisolid and solid-state material etc. all can be used for practice of the present invention.Electrochromism conversion medium 33 can be the electrochromic media of liquid phase type, and wherein, when electrochemically being reduced or during oxidation (comprising gel), the material that is included in the solution with the electrolyte form of ionic conduction is retained in the solution with electrolytical form.Electrochromic media 33 optionally can be the electrochromic media of confined surfaces, wherein when electrochemically being reduced or during oxidation, directly is adhered to conductive electrode or restriction material in its vicinity keeps adhering to or restriction.Alternatively, electrochromic media 33 can be an electro-deposition type electrochromic media, and wherein when electrochemically being reduced or during oxidation, the material that is included in the solution with the form of ionic conductivity electrolyte forms one deck on conductive electrode.
Although do not limit the present invention, but in a non-limiting example, electrochromic media 33 comprises at least two kinds of compounds, comprise at least a anode electrochromic compounds and at least a cathodic electrochromic compound component, anode compound is represented oxidizable material, and cathode compound is represented reducible material.When electrochromic media 33 applies voltage, the oxidation of anode electrochromic compounds, cathodic electrochromic electrochromic compound reduction simultaneously.The redox of this while causes changing the absorption coefficient of at least one wavelength in the visible spectrum when electrochemically being activated.When voltage was applied to the two ends of electrode 38 and 40, the combination of anode in the electrochromic media 33 and cathodic electrochromic electrochromic compound determined relative color.The former dyestuff of the so-called purple of this cathodic electrochromic electrochromic compound (viologen dyes), and the so-called phenazine dyes of this anode electrochromic compounds.
In another non-limiting example of the present invention, electrochromism conversion medium 33 can change transmissivity when it applies voltage.The voltage that applies can be optionally, makes electrochromism conversion medium 33 can selectivity also activate changing the color of medium, thereby changes the transmissivity of electrochromic media.By this way, medium 33 can be when not applying voltage a transmissivity rank and conversion between the second transmissivity rank when applying voltage.Preferably can be self-purging in this variable color that applies and do not apply medium between the electric state, the electrochromism active state that makes its electrochromic media variable color when applying voltage therein, and wherein electrochromic media returns or returns to conversion between the electrochromism disactivation state of its colourless state automatically when removing voltage.In a non-limiting example of the present invention, these characteristics are easy to by providing switch 168 (seeing Fig. 7 A) or variable output configuration 170 (seeing Fig. 7 B) to realize.
In another non-limiting example of the present invention, the color of conversion medium 33 can be normal dark or dark when applying voltage, perhaps can change dark or dark degree when voltage changes.For example, the darkness of concrete variable color or variable color can change between the scope of voltage and power density.When low power density imposed on medium 33, medium 33 can begin variable color.Increasing voltage can cause the color blackening of dyestuff to dark darkness or brightness.By this way, medium 33 can comprise when voltage changes light transmission in various degree, thereby can adjust to the darkness or the shade strength level of expectation according to the voltage that it applied.This can realize by the variable transformer that use is used for the switch between bus-bar and power supply, for example but do not limit the present invention, is used for switch 168 (referring to Fig. 7 A) or variable voltage output configuration 170 (referring to Fig. 7 B).In a non-limiting example of the present invention, electrochromic media 33 conversion between 1% to 80% transmission of visible light scope.Like this, electrochomeric glass of the present invention can be effectively as the opaque shade of window.
In another non-limiting example of the present invention, the medium of electrochomeric glass of the present invention or unit is disposable and non-self-purging, make voltage application cause electrochromic media 33 variable colors, and electrochromic media remain on the variable color state up to voltage reversal or diminish (shorten).
The electrochromism conversion medium is known in the field, for example but do not limit the present invention, and referring to U.S. Patent No. 5,202,787; 5,805,330; 6,747,779; 6,828,062 and 6,667, the 825 additional descriptions about electrochromic media, this electrochromic media can together use with electrode of the present invention.
In a non-limiting example of the present invention, electrochromic switchable cell of the present invention or glass can be made in the following manner.Adopt MSVD technology, sputtering electrode 38 on the inside surface 42 of glass sheet 35, and on the inside surface 42 of glass sheet 36 sputtering electrode 40.In the sheet 35 and 36 each is 4 inches squares (10.16 squares centimetre) glass sheet, and each in the electrode includes to have calculates by weight 52% zinc and 48% tin, has the first zinc stannate dielectric film 74 of 336 dust thickness on the inside surface 42 that is deposited on glass sheet 35 and 36; Has first Zinc oxide film 72 that is deposited on 85 dust thickness on the first zinc stannate film 74; Has first silverskin 68 that is deposited on 220 dust thickness on first Zinc oxide film 72; Has the first bronze medal diaphragm 88 that is deposited on 8 dust thickness on the silverskin 68.For conductive layer 94A, the indium oxide tin film with 700 dust thickness is deposited on the first bronze medal diaphragm 88, and for resistive formation 94B, has second film 74 of calculating by weight 52% zinc and 48% tin and 700 dust thickness and be deposited on the first bronze medal diaphragm 88.Second Zinc oxide film 72 with 85 dust thickness is deposited on layer 94A or the 94B; Second silverskin 68 with 220 dust thickness is deposited on second Zinc oxide film 72; The second bronze medal diaphragm 82 with 10 dust thickness is deposited on second silverskin 78, and the indium oxide tin film 80 with 373 dust thickness is deposited on the second bronze medal diaphragm 82.Have sputtering electrode glass sheet each all expect to have transmission of visible light greater than 55%, and the expectation of the surface of the tin indium oxide of contact medium 33 has the sheet resistance of 2.4 ohm of every squares.
Be placed on the inside surface 30 of electrode assemblie 22 at the preformed polymerization spacer element 29 that has bonding coat on the top and bottom face of sept 29.The inside surface 32 of electrode assemblie 24 is placed on the bonding coat of spacer element opposite side, and electrode assemblie 22 and 24 pushed toward each other, thereby and bonding coat solidify the chamber 34 that sealing is provided.
The electrochromic media 33 that has greater than liquid phase type 70% transmission of visible light, that use this area pours into filled chamber 34 by the hole in the spacer element 29 46.After chamber 34 fills up, with this hole of adhesive seal.Then, as shown in Figure 7 bus-bar 142,144,146,148,150 and 152 is connected to electrode 38 and 40, be used to have the glass of resistive formation 94B, and as shown in Figure 5 bus- bar 114 and 116 be connected to electrode 38 and 40, be used to have the glass of conductive layer 94A.These bus-bars are connected to power supply, as mentioned above.
In a non-limiting example of the present invention, when the bus-bar of glass is not powered and electric current when not flowing through medium, as mentioned above, the expectation of the viewing area of electrochomeric glass has the transmission of visible light in 60~75% scopes.Like this, electrochomeric glass is in pellucidity.When the bus-bar of glass is powered and electric current when flowing through medium, the viewing area expectation of glass deepening and glass has about 0~1% transmission of visible light.Electrode and power supply disconnect and make electrochromic media 33 beginning self-cleanings, thereby allow glass turn back to its initial pellucidity.
When electric power imposes on the bus-bar 142 of the glass with layer 94B and 144 the time, sheet 35 is heated, and when electric power imposed on bus- bar 146 and 148, sheet 36 was heated (referring to Fig. 7 and Fig. 7 A), as mentioned above.
Shown in Fig. 8 is the non-limiting example with aircraft glass 180 of electrochromism conversion glass of the present invention (for example, glass 20,100 or 140).Show the lateral direction of the relative aircraft glass 180 of aircraft with arrow 182, show the interior side direction of the relative aircraft glass 180 of aircraft with arrow 184.The outside pane module 181 that comprises the aircraft glass 180 of electrochromism conversion glass of the present invention adds assembly 188 to keep in the face of concerning with the substantially parallel isolated of optional vibration damping/acoustic absorption pane module 186 by the interval box that forms space 190 betwixt.Interval box adds assembly 188 and comprises that the aluminium frame adds 192, and it surrounds rubber layer 194, and this rubber layer keeps outside pane module 181 to be in spaced relationship with vibration damping/acoustic absorption pane module 186.The 190 sealed places in the space, this space can use insulating gas (such as, air, argon gas, krypton gas or its mixture) all or part of filling.Protection internal layer (not shown among Fig. 8) normally is arranged on spacing frame assembly 188 inboards, contacts with pane module 186 physics preventing.Can be for the detailed argumentation of spacing frame assembly 188 and vibration damping/acoustic absorption pane module 186 with reference to U.S. Patent application No.5,965,853, this application is by with reference to being incorporated into this.Outside pane module 181 comprises electrochromism conversion glass of the present invention and is arranged to provide the additional plastic and glass sheet of the outside pane module of all safety requirements that satisfy aircraft glass.For example but do not limit the present invention, outside pane module 181 comprises electrochromism conversion glass of the present invention, and can comprise two or more glass or plastic pane alternatively, it can also comprise one or more interlayers that are located between the pane, or laminated product can comprise that the combination of single pane and one or more lamination sandwich material thereon is to form outside pane module 181.Glass pane can be by chemistry or hot tempering.The plastic pane that is fit to comprises cast acrylic (cast acrylics), the acrylic acid and the polycarbonate that stretch.The sandwich material that is fit to comprises polyvinyl butyral, polyurethane, silicones and combination thereof.As selection, electric driven color-changing part can be independent of outside pane module 181.More specifically, assembly 181 can comprise one or more plastics and/or glass sheet, and the type of the electrochomeric glass of argumentation can be positioned in the space 190 here, separates with assembly 181.Such as the skilled artisan will appreciate, electrochromism conversion glass of the present invention also can be merged in outside pane module 181 and the vibration damping/acoustic absorption pane module 186 that vibration damping/acoustic absorption pane module 186 maybe can be independent of aircraft glass 180.
As now understandable, the present invention does not limit the article that wherein can use electrode of the present invention.More specifically,, show another non-limiting example of the present invention, electrode of the present invention is used for mirror 210, for example but do not limit the present invention, the inside rear view mirror of the vehicles or external mirror having indicator light, or bathroom mirror with reference to Fig. 9.Mirror 210 comprises sheet 35 and electrode assemblie 24, and wherein sheet 35 has reflectance coating 212 on the inside surface 42 of sheet 35, and electrode 220 is on reflection horizon 212.In a non-limiting example of the present invention, electrode 220 is included in the active layer 62 on the dielectric layer 66 of basic unit 60 and is connected in the bus-bar 150 of active layer 62.
Such as will be appreciated, because sheet 35 has reflectance coating 212 on inside surface 42, so sheet 35 can be transparent or opaque, and is made by any material, for example but do not limit the present invention, wood, glass, metal, plastics or its combination.Randomly, reflectance coating 212 can be arranged on the outside surface 44 of sheet 35.In this case, sheet will be transparent, for example have the transmission of visible light greater than 60%.The deposition of reflective coating is well known in the art with cremasteric reflex surface or minute surface on substrate, and need further not discuss about reflectance coating 212.
Such as will be appreciated, the present invention's expectation makes electrode 38 replace electrode 220 to use.In this example, electrode 38 comprises the articulamentum 90A (as shown in Figure 4) with conductive layer 94A and is electrically connected to active layer 62 and the bus-bar 114 of the first metal layer 68 of basic unit 60 (also referring to Fig. 4) (at first shown in Fig. 5 B).
With reference to Fig. 7 A and Fig. 9, in a non-limiting example of the present invention, in order to reduce dazzle from the light of the back vehicles, switch 168 closures, and the electric current to bus- bar 152 and 150 is disposed by variable voltage output, for example the variable voltage shown in Fig. 7 B is exported configuration 170 and is changed, thereby reduces the transmission of visible light of medium 33.Accumulate in the moisture on the outside surface 44 of sheet 36 of mirror 210, thereby for example snow, mist, the globule and/or ice make electric current remove by metal level 68 heating mediums 33 and sheet 36 by Closing Switch 163, as mentioned above.
Electrode assemblie does not comprise reflectance coating 212, but the electrode assemblie that makes comprises the electrode 220 that is positioned on the glass sheet.The electronic package that makes is used to make spendable electrochromism conversion glass.
The non-limiting example of electrode 220 comprises: on the reflection horizon 212 or the ground floor 66 on the inside surface 42 of sheet 35, and the metal level 78 on the ground floor, protective seam 82 on the metal level 78 and the conductive metal oxide layer 80 on the protective seam.Such as will be appreciated, the electrode 220 of mirror 210 can replace with the electrode on the reflection horizon 212 38.In this example, use bus-bar 114 (referring to Fig. 5 B) and omit bus-bar 110 (referring to Fig. 5).
And, as now understandable, the present invention does not limit the quantity of the metal level that electrode has, metal level 68 and 78 for example, and electrode of the present invention can comprise having with conductive metal oxide layer 80 and together uses active layer 62 (referring to Fig. 4) with the two-layer or multiple layer metal layer 78 that increases the electric current flow velocity by medium 33, and/or basic unit 60, thereby this basic unit has two-layer or multiple layer metal layer 68 improves the heating-up temperature of basic unit 60 with the electric current that increases basic unit 60 two ends.
Based on the description of the embodiment of the invention, be appreciated that to the invention is not restricted to disclosed specific embodiment, but its intention is encompassed in the modification in the spirit and scope of the invention that is defined by the following claims.
Claims (29)
1. electrochromic switchable cell comprises:
First electrode assemblie has the electrode that is defined as first electrode;
Second electrode assemblie has the electrode that is defined as second electrode, and wherein first and second electrodes are in opposed facing relation;
Medium between first and second electrodes, this dielectric response electric excitation and change number percent through the visible light of this medium;
First electrode assemblie has first first type surface in the face of this medium, and wherein first electrode is between first first type surface and this medium, and described first electrode comprises:
First conductive layer between this medium and first first type surface;
And first conductive layer is spaced apart and second conductive layer between first conductive layer and this medium;
The conduction articulamentum that between first conductive layer and second conductive layer and with first conductive layer, is connected with second conductive layer;
Be spaced from each other and contact first and second contact parts of first conductive layer, wherein, first and second contact parts and first conductive layer provide first conductive path, and
Contact the 3rd contact part of second conductive layer, and
Contact the 4th contact part of second electrode, wherein, third and fourth contact part, second conductive layer, this medium and second electrode provide second conductive path.
2. electrochromic switchable cell according to claim 1, wherein, described medium is the electrochromism conversion medium, and the wavelength in 400~700 nanometer range is transparent during at least one electrode assemblie.
3. electrochromic switchable cell according to claim 1, wherein, first first type surface of current flow heats first electrode assemblie by first conductive layer.
4. electrochromic switchable cell according to claim 1, wherein, the first and the 3rd contact part all is connected respectively in the positive terminal of direct supply and the negative terminal, and second all is connected the described positive terminal of direct supply and in the negative terminal another respectively with the 4th contact part.
5. electrochromic switchable cell according to claim 1, wherein, first and second contact parts are connected to first direct supply, and third and fourth contact part is connected to second direct supply.
6. electrochromic switchable cell according to claim 1, wherein, second electrode assemblie has the first type surface that is defined as in the face of second first type surface of described medium, and wherein second electrode is between second first type surface and described medium, and described second electrode comprises:
Between the described medium and second first type surface, be defined as the conductive layer of the 3rd conductive layer;
And the 3rd conductive layer is isolated and be defined as the conductive layer of the 4th conductive layer between the 3rd conductive layer and described medium;
Contact the 4th contact part of the 4th conductive layer; And
Be spaced from each other and contact the 5th and the 6th contact part of the 3rd conductive layer, wherein, the 5th and the 6th contact part and the 3rd conductive layer provide the 3rd conductive path.
7. electrochromic switchable cell according to claim 6, wherein, described medium is the electrochromism conversion medium, first contact part comprises first bus-bar that is connected to first conductive layer, second contact part comprises second bus-bar that is connected to first conductive layer, the 3rd contact part comprises the 3rd bus-bar that is connected to second conductive layer, the 4th contact part comprises the 4th bus-bar that is connected to the 4th conductive layer, the 5th contact part comprises the 5th bus-bar that is connected to the 3rd conductive layer, and the 6th contact part comprises the 6th bus-bar that is connected to the 3rd conductive layer.
8. electrochromic switchable cell according to claim 1, wherein, described medium is that the electrochromism conversion medium and first electrode assemblie pass through the wavelength in 400~700 nanometer range.
9. electrochromic switchable cell according to claim 8, wherein, described conduction articulamentum has the predetermined resistance to the electric current that flows along first conductive layer, makes at least 50% the electric current that flows along first conductive layer arrive second conductive layer by described conduction articulamentum.
10. electrochromic switchable cell according to claim 9, wherein, first contact part is the bus-bar that provides electric current to be connected simultaneously for first and second conductive layers with the 3rd contact part.
11. electrochromic switchable cell according to claim 9, wherein, first contact part comprises first bus-bar, and second contact part comprises second bus-bar, and the 3rd contact part comprises the 3rd bus-bar.
12. electrochromic switchable cell according to claim 1, wherein, described medium is the electrochromism conversion medium; First electrode assemblie is by the wavelength in 400~700 nanometer range; First first type surface is first first type surface of transparent substrates; First conductive layer comprises the first metal layer; And second conductive layer comprises first conductive metal film and second conducting film that electrically contacts with described medium, and described first electrode also comprises:
Substrate contact layer between first first type surface of the first metal layer and described substrate,
Wherein said conduction articulamentum is between first metal film of the first metal layer of first conductive layer and second conductive layer.
13. electrochromic switchable cell according to claim 12, wherein, described substrate is a glass sheet, described glass sheet also comprises and the first first type surface opposite second major surface, and be included in coating at least one first type surface of glass sheet, this coating from hydrophobic coating, hydrophilic coating, anti-solar control coating and in conjunction with select.
14. electrochromic switchable cell according to claim 12, wherein, closed frame is being connected between the described electrode assemblie and with described electrode assemblie providing sealed chamber between described electrode assemblie, and described medium comprises the electrochromism conversion medium.
15. electrochromic switchable cell according to claim 12, wherein, this electrochromic switchable cell is used for:
The land craft that the glass of the type of vehicle that A selects from following group: a selects from the group of the combination of automobile, truck, car, motorcycle, train and above-mentioned car; The b aircraft; The c spacecraft; The d marine communication means; The combination of the e underwater vehicle and the above-mentioned vehicles of f;
The window of the structure that B selects from following group: a residential building; The b commercial building; The c oven door; The d door for microwave oven; The e refrigerator doors; Combination with the f said structure;
The C mirror;
D vehicles rearview mirror;
E vehicles side-view mirror; And
The combination of the above-mentioned A to E of F.
16. electrochromic switchable cell according to claim 12, wherein, described substrate contact layer comprises supporting layer and metal contact layer.
17. electrochromic switchable cell according to claim 16, wherein, the supporting layer of described substrate contact layer comprises the zinc stannate film, and the metal contact layer of described substrate contact layer comprises Zinc oxide film, and the first metal layer of first electric contacting layer comprises the silverskin that is defined as first silverskin.
18. electrochromic switchable cell according to claim 17, wherein, the zinc stannate film is positioned on first first type surface of described substrate, and Zinc oxide film is positioned on the zinc stannate film, and first silverskin is positioned on the zinc oxide film.
19. electrochromic switchable cell according to claim 18, wherein, described conduction articulamentum is the conduction articulamentum that makes the first metal film electrical interconnection of first silverskin of first conductive layer and second conductive layer.
20. electrochromic switchable cell according to claim 19, wherein, described conduction articulamentum is the conduction of current layer, passes to first metal film of second conductive layer with at least 50% electric current of first silverskin that will impose on first conductive layer.
21. electrochromic switchable cell according to claim 20, wherein, described conduction articulamentum comprises supporting layer and metal contact layer.
22. electrochromic switchable cell according to claim 21, wherein, the supporting layer of described conduction articulamentum is the zinc stannate film, and the metal contact layer of described conduction articulamentum is a zinc oxide film, and first metal film of second conductive layer is the silverskin that is defined as second silverskin.
23. electrochromic switchable cell according to claim 22, wherein, second film of second conductive layer is a conducting metal oxide, and the zinc stannate film of described conduction articulamentum is positioned on first silverskin, the Zinc oxide film of described conduction articulamentum is positioned on the zinc stannate film of conduction articulamentum, second silverskin is positioned on the Zinc oxide film of described conduction articulamentum, and second film of second conductive layer is positioned on second silverskin.
24. electrochromic switchable cell according to claim 19, wherein, described conduction articulamentum comprises the diaphragm and the conductivity ceramics film that is positioned on this diaphragm on the first metal layer that is positioned at first conductive layer.
25. electrochromic switchable cell according to claim 24; wherein; protective seam is the anoxic sputter ceramic membrane on the first metal layer, and the conductivity ceramics film is to be positioned on the anoxic sputter ceramic membrane and sputter ceramic membrane that have the oxygen of Duoing than described anoxic sputter ceramic membrane.
26. electrochromic switchable cell according to claim 12 also is included on the first metal layer of first conductive layer and the protective seam on first metal film of second conductive layer.
27. electrochromic switchable cell according to claim 26, wherein, the protective seam at least one in first metal film of the first metal layer of first conductive layer and second conductive layer is an anoxic sputter ceramic membrane.
28. electrochromic switchable cell according to claim 26; wherein, the combination of protective seam selected among zirconium, titanium, copper, metal oxide, metal nitride, non-stoichiometric ceramics, titanium nitride and the above-mentioned material at least one in first metal film of the first metal layer of first conductive layer and second conductive layer.
29. method that operates in the electrochromic switchable cell of the type that has the first transparency electrode assembly on the first type surface, first electrode assemblie and second electrode assemblie are spaced apart, and the electrochromism conversion medium is between first and second electrode assemblies, and this method may further comprise the steps:
First electrode assemblie is provided, described first electrode assemblie have first conductive layer spaced apart with first type surface and that electrically contact with the electrochromism conversion medium, between first conductive layer and the first type surface and with first conductive layer and isolated second conductive layer of electrochromism conversion medium and the conduction articulamentum that between first conductive layer and second conductive layer and with first conductive layer, is connected with second conductive layer, and
In seclected time, make electric current pass through first and/or second conductive layer,
Wherein, first conductive layer is that the first metal layer and second conductive layer are second metal levels, and provides the step of at least one electrode assemblie may further comprise the steps:
First dielectric layer is provided on first type surface;
Second metal level is provided on first dielectric layer;
Described conduction articulamentum is provided on second metal level;
On described conduction articulamentum, provide the first metal layer; And
Conductive metal oxide layer is provided on the first metal layer,
Wherein, in the step of seclected time, make electric current pass through second metal level, and make electric current pass through the first metal layer, thereby change the transmission of visible light of medium so that electric current arrives second electrode assemblie by electrochromic media with the heating first type surface.
Applications Claiming Priority (5)
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US69606605P | 2005-07-01 | 2005-07-01 | |
US60/696,066 | 2005-07-01 | ||
US11/472,334 US7586664B2 (en) | 2005-07-01 | 2006-06-22 | Transparent electrode for an electrochromic switchable cell |
US11/472,334 | 2006-06-22 | ||
PCT/US2006/024800 WO2007011499A2 (en) | 2005-07-01 | 2006-06-26 | Transparent electrode for an electrochromic switchable cell |
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CN101322069A CN101322069A (en) | 2008-12-10 |
CN101322069B true CN101322069B (en) | 2010-09-22 |
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CN2006800234328A Expired - Fee Related CN101322068B (en) | 2005-07-01 | 2006-06-26 | Transparent electrode for an electrochromic switchable cell |
CN200680023433A Expired - Fee Related CN100582908C (en) | 2005-07-01 | 2006-06-26 | An electrochromic vision panel having a plurality of connectors |
CN2006800234722A Expired - Fee Related CN101322069B (en) | 2005-07-01 | 2006-06-26 | Transparent electrode for an electrochromic switchable cell |
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CN2006800234328A Expired - Fee Related CN101322068B (en) | 2005-07-01 | 2006-06-26 | Transparent electrode for an electrochromic switchable cell |
CN200680023433A Expired - Fee Related CN100582908C (en) | 2005-07-01 | 2006-06-26 | An electrochromic vision panel having a plurality of connectors |
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Also Published As
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CN101300523A (en) | 2008-11-05 |
CN101322068B (en) | 2010-09-22 |
CN101322068A (en) | 2008-12-10 |
CN100582908C (en) | 2010-01-20 |
CN101322069A (en) | 2008-12-10 |
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