CN1207182A - Apparatus and method for assembling electrochromic cells - Google Patents
Apparatus and method for assembling electrochromic cells Download PDFInfo
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- CN1207182A CN1207182A CN 97191559 CN97191559A CN1207182A CN 1207182 A CN1207182 A CN 1207182A CN 97191559 CN97191559 CN 97191559 CN 97191559 A CN97191559 A CN 97191559A CN 1207182 A CN1207182 A CN 1207182A
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Abstract
Apparatus and methods for manufacturing electrochromic cells. Layers of various inks are printed on substrates by high speed printing means. The electrochromic cells comprise layers of electrode (26), electrolyte (28), and counter electrode (30) ink materials which are printed on at least one substrate (54). When an electrical voltage differential is introduced between the electrode and counter electrode layers, an electrochemical reaction occurs in the electrochemical cell.
Description
Technical field
The present invention relates generally to make electrochromic device, relate in particular to the apparatus and method of group device electrochromic cells, when this unit is subjected to encouraging, the visible variation of generation state, and applicable to multiple device.
Background technology
Proposed the electrochromic cells of various designs, be used for the different device of such class, comprising such as graphic presentation watch displays, variable transmission window and mirror and be used for cell voltage or the indicator of charged state etc.Though their concrete structure can have significant change with their purposes, most of electrochromic devices have several common characteristic.Generally say, electrochromic device is made up of electrochemical cell, and this electrochemical cell has first conductive electrode as negative electrode, as second conductive electrode of anode and so as to first and second electrodes being got in touch so that realize the media of visible change in the unit when DC voltage being applied on the circuit that comprises first and second electrodes.Usually the form that presents solid, semisolid or liquid electrolyte so as to the media that all electrodes are got in touch.Electrode and electrolytical any one can comprise electrochromic material, the electric current that it causes in response to applying DC voltage is so that produce desirable variation in the unit.
The work of electrochemical cell can produce permanent or reversible ionization or deionization to the metal that is included in electrolyte and/or at least one electrode, and the latter causes oxidation or reduction (redox) reaction on respective electrode.The space of this unit is restricted usually, and wherein first and second electrodes may be separated together with an escapement each other by electrolyte.In addition, this unit comprises the substrate that can be made by the flexibility or rigidity material usually at least, by substrate, can observe occurent metal deposition or dissolving in this battery.For example, if if substrate be substantially transparent or substrate comprise aperture or the window that can observe visible change, then just can observe visible change in the unit by this substrate.
Comprise U.S. Patent number 4,116,535,4,188,095,4,285,575 and 4,902,108 by having the example of rigid substrate with the electrochemical device that closed cell is formed of the liquid electrolyte that first and second electrode is got in touch.
U.S. Patent number 5,411,817 have disclosed a kind of battery charge indicator, and wherein, the layer between the pair of electrodes includes antioxidant, photograph colorant dispersion and photograph developer.Also disclosed the various possible component of this layer, but in described limited field just now, the neither one patent discloses and show that possessing the electrochemical process that makes the electrolyte color conversion therein is reversible effect under nonreversible polarity of electrode.It is irreversible that some other application that is disclosed, for example disposable ammeter and " phonecard " etc. all show the hint electrochemical process.
U.S. Patent number 3,720,869 have disclosed the method for electrode charged state condition in a kind of definite battery, and it is determined by the resistance of measuring the battery electrode of changing between metal and nonmetal attitude.
U.S. Patent number 3,667,039 has disclosed a kind of measuring instrument that uses liquid crystal cell, and it shows visible variation in response to the input signal that is higher than given threshold level.
Several United States Patent (USP)s of authorizing Warszawski have disclosed optical modulation device and manufacturing or have used the method for this optical modulation device.These United States Patent (USP)s are 5,054,894,5,056,899,5,074,648,5,078,480,5,080,470 and 5,082,355.All these six substances that patent disclosed are in fact all identical.Therefore, for the sake of simplicity, below these patents are referred to as " Warszawski patent ".
About realizing several dissimilar optical modulation devices, for example in overall situation, such as the large-scale signboard of public place, the Warszawske patent has disclosed many embodiment.These patents emphasize to keep the structural integrity of the optical modulation device that discloses, especially under the situation of large-scale device, so that the interface of electrolyte-electrode can not be subjected to the undue influence of local interruption and/or stress.
For this reason, the Warszawski patent propose to be used the dielectric substrate between the comparative electrode, keeps the compliance of height, and to propose electrolyte particularly be plasticity or viscoelastic.Equally, in order to remain on structural combination, proposing electrolyte layers or possessing has independent bonding agent, or self-adhering-type, to guarantee suitably bonding with all electrodes.
Though the Warszawski patent is represented to plan to use the electrode that needs not to be flat, do not have instruction or suggestion to give electrode itself and have submissive effect.Therefore, it seems the Warszawski patent,, should suppose that electrode that side and dielectric substrate (all layer) join comes down to rigidity though plan to use submissive dielectric substrate.Under the situation of large-scale public signboard, this will appear is especially true.
About making the optical modulation device that the Warszawski patent is disclosed, different technology has been proposed, such as thick film application technology and cut-out (cut-out) technology.The thick film application technology relates to correlation techniques such as serigraphy, air gap, spiral curve.The cut-out technology for example relates to, and production comprises the complex with electrolytical electrode and then complex is added on another electrode.The technology of planning to use is such as extruding, roll extrusion, calendering, coating etc., and punching, punching press and cut etc.
U.S. Patent number 4,497,881 have described a kind of battery charge indicator, and it comes down to be formed by the parts that are present in the battery self.Specifically, in battery, be provided with generation and obviously can constitute the compound of electrolyte, anode gel, cathode material or the charging of two or more these compound combinations.The charging of this generation compound just is arranged on the outer cylinder surface of battery case, and the color of configuration use appointment, when battery is full of electricity, be black for example, and when battery charge has been consumed, then change over different colors gradually, for example grey.The outside surface of battery case is provided with aperture or window, sees the color of the charging that produces compound can make the user.As if this patent is emphasized to use already present material in conventional batteries, and does not add the compound or the structure of indication color in addition.
United States Patent (USP) 4,917,973 have disclosed a kind of secondary cell, and wherein battery itself electrode changes color according to the voltage between the battery positive and negative electrode.Window or aperture are set, so that see the change color of above-mentioned electrode.It seems that this patent only be limited to secondary cell, also is the small-sized battery that is generally dish type.
U.S. Patent number 5,256,500 have lectured a kind of battery such as lithium battery, and it has built-in life indicator.This patent is primarily aimed at lithium battery, but also this invention of being disclosed of expection also can with the battery of other type, for example manganese cell and nickel-cadmium battery etc. are used in combination.Usually the part of suggestion " indicator elment " conduct " life indicator " is arranged in the battery self.Expection has various types of indicators, and for example electric driven color-changing part, electricity ring unit and liquid crystal cells etc.In one embodiment, with respect to the positive plate container of battery, " life indicator " can be chosen to can install with dismountable.In this mode, can have only in the time will reading just life indicator to be installed on the battery.For this embodiment, seemingly select to install with dismountable by meshing with above-mentioned positive plate container threads.Do not disclose other possible embodiment that can take off life indicator.
United States Patent (USP) 5,250,905,5,396,177,5,339,024,5,418,086 has described the battery with the electro-chemical test device that is installed in the outside with disclosed PCT application PCT/US92/07757 (international publication number WO/93/06474) from different aspects.Test component itself comprise more following essential electrochemical cells parts, be cathode electrode, electrolyte and be arranged on and directly adhere to the anode electrode in the label on the battery case.In each piece list of references, test component and battery terminal are always parallel connected at these, to enable to read continuously the electriferous state of battery.Under the effect of applying DC voltage, electriferous state is determined according to the consumption or the dissolving of anode electrode.Tester also comprises electrolyte, and it can be a solid, also can contain the porous polymeric membrane array of electrolyte solution.If solid, then electrolyte may be too crisp, so that be unable to undergo power that the outside applies and the mechanical shock that is subjected in battery normal transport, loading and unloading and use.In these environment, solid electrolyte may be broken, thereby worsened the contact between the electrode, makes tester ineffective.On the other hand, when forming membrane array, must pre-form electrolyte, in the different manufacturing step that separates, be added on the electrode then, thereby make the label manufacture process become complicated and time-consuming and increase its expense.
United States Patent (USP) 5,418,085 and 5,494,496 have described a kind of electrochemical cell tester spare, it can overall fixed to an end of battery.These lists of references have usually been discussed electrochromic material, can be printed onto these materials on the substrate, how to print these materials down to produce the details of the device that can work actual creating conditions but lecture particularly.More particularly, the preferable composition of electrochromic material and how to select these materials and/or carry out reliably when how to make it to be suitable for normally to make, load and transport and use at battery is not discussed basically.Also whether these materials are effective when being disclosed in the test label that stands around the battery context, and bigger, more frequent mechanical shock is generally born than battery terminal in that zone.
United States Patent (USP) 5,458,92 have lectured a kind of electrochromism battery testing device, and it can be combined in the battery label that is attached on the battery case cylindrical wall.The electrolyte part of the electrochromism tester that this patent disclosed can be solid or thickened solutions.If solid, then electrolyte may stand the fragmentation of generation inefficacy when label and battery are normally made, transport, loaded and unloaded and use as mentioned above.If form thickened solutions, can not guarantee that then solution keeps its electrolyte characteristic during the whole available service life of battery, especially become dry when solution, and more like this when being essential for the threshold level that keeps electrolysis in electrolyte vitality active and electrochromic cells that accompanies to continue existing humidity.With reference to general document, it takes the printed label substrate by what utilize conduction with electrochemical activity printing ink or paint to the method for assembling electrochromic cells.Yet except the discriminating of some active material and thickening agent, do not disclose these materials of combination and be fit to concrete grammar or the prescription of high speed printing with feasible printing ink or paint to produce.
Therefore, the method and apparatus that can constitute the film electrochromic cells that be added to one or more flexibility or rigidities on-chip a series of preferably non-preformed layers cheap for high-speed production has an advantage, wherein each layer of these layers all can be deposited by coating or printing equipment, and comprising arbitrary electrode and dielectric substrate at each interior layer during the whole available service life of electrochromic device that the unit is used whereby, the 26S Proteasome Structure and Function characteristic when all keeping them to apply.
Though Modern High-Speed printing and paint-on technique have appeared to provide the approximate means of producing electrochromic cells, when constructing electrochromic cells, there is important problem to overcome with this means.For example, every kind of figure and be conclusive in particular for the component of the functional ink that constitutes the unit, but this is because the component of printing ink has determined their electricity, chemistry and mechanical property and printing characteristic, but also because printing ink solvent produces disadvantageous reaction with the substrate material that is applied with printing ink sometimes.Because these difficulties, traditional printing and coated product, technology and device still can not be used for being assembled with functional and reliable electrochromic cells so far.
Therefore, the film electrochromic cells that needs technology a kind of general-purpose, at a high speed, economic and device manufacturing to be used for various devices.Also need some technologies, device and electrochromic material like this, have electrochromic cells and/or the device that mark is accepted face, on this surface, can add permanent or temporary transient color graphics, and not influence the function of electrochromic cells with production.
Summary of the invention
The present invention comprises the prefabricated all layers of a series of best right and wrong of a kind of usefulness and is added to the method and apparatus that constitutes electrochromic cells on one or more flexibility or rigidity substrates, and wherein, each layer in these layers all can be by coating or printing technology deposit at a high speed.The functional layer of electrochromic cells is applicable to makes printing ink or have ink characteristics and/or the material of feature (being referred to as " printing ink ") that wherein every kind of printing ink partially or completely becomes dry, to form solid or semi-solid layer at this.The present invention also comprises the economic means of making various film electrochromic cells and/or film electrochromic device, and these devices comprise electrochromic cells (being referred to as " electrochromic cells " or " unit " here).The present invention also comprises the general-purpose device, and it can be used to produce the electrochromic cells that comprises function and/or graphic elements and the device of various structures.
Method and apparatus of the present invention is applicable to any typography, for example serigraphy, sputter, relief printing plate, aniline printing, lithographic printing, hectographic printing, tulle printing or intaglio printing.Any printing in these printing technologies can be used for producing electrochromic cells or device.On the other hand, also can use in these printing technologies two kinds or multiple printing technology to produce electrochromic cells or device.
For realizing purpose of the present invention, a kind of preferable printing process is intaglio printing.Intaglio printing use or flat board or printing cylinder, they include and are used for printing ink is added to desirable on-chip so-called " image-carrier ".The image-carrier that uses in the image-carrier that uses in the intaglio printing and other printing process is different, and this is because the image of intaglio plate image-carrier is that engraving or corrosion are come out below the non-image areas surface of image-carrier.Intaglio printing is used to print currency and replica.Though high-quality printed matter is produced in intaglio printing, the printing ink that high viscosity is arranged is used in this offset printing, needs very high pressure to come being transferred on the substrate on the image slave plate.
Therefore, be preferably at present and use printing cylinder, it is urinated in being transferred to any on-chip printing ink of wishing with viscosity.Printing cylinder of the present invention can be carved, and optionally chemical corrosion then (below will describe in further detail) deposits to the quantity of ink on arbitrary certain layer of electrochromic cells with increase.
The image of biting and being carved out on the cylinder.Sculptured surface has 2000 to 9000 unit of being carved the surface approximately per square inch.The actual size of unit and quantity are decided by the density of the required printing ink of final printed images.Decompose all images to the silk screen screen, make the image of engraving might hold low-viscosity liquid ink, up to having added printing ink.The printing of use the typography of this engraved roll to be called " rotogravure " or " intaglio plate ".
Because of its denseness of holding and adaptability in the application of repeating print that needs denseness and inhomogeneity application or printed layers, so rotogravure printing is preferably.Present rotogravure pressman skill mainly concentrate on relative simple technology with on the relevant traditional oils ink material of printed pattern colored ink on the various substrates.The present invention is equally also at these technology, and introduced some novel methods, device and the material of printing-ink, and this printing ink includes the functional part of electrochromic cells.
The image-carrier that uses in rotogravure pressman skill comprises a cylinder with steel core or aluminium core usually.This fuse is electroplated with copper, and to carve with the opposite of wanted printed pattern, so that " image-carrier district " (zone of ink deposition before using) is in below the surface of cylinder.Then to whole cylinder chromium plating, to improve the serviceable life of engraving.
The inventor observes, can not deposit the various printing ink that constitute needed enough capacity of film electrochromic cells and thickness for traditional graph printing purpose with the printing cylinder that rotogravure adopted.Printing cylinder of the present invention has overcome these deficiencies, and it at first carries out electronic engraving, uses for example acid (such as HCL) or other class etch recipe to carry out chemical etching then, makes each image-carrier district produce suitable capacity and shape.
Chemical etching increases total capacity by increasing the surface area of carving the unit that forms in the engraving part in image-carrier district.Therefore, the thickness of the printing cylinder of the chemical etching ink lay that can deposit and uniformity coefficient will only the ink lay through mechanical etched cylinder deposition be thicker, more even than using.
Rotogravure comprises one or more printing units usually, and wherein each printing machine generally comprises carved image carrier cylinder, ink fountain, doctor blade, impression ink roller and ink setting device.Along with the cylinder rotation, printing ink is coated onto on the column figure carrier from ink fountain, and doctor blade erasing cylinder surface, before printing, to clean.Printing ink wait to deposit thereon substrate by cylinder and the impression ink roller between.Cylinder contacts with this substrate with ink roller, and the location, so that pressure is added on the substrate, impels the printing ink transfer printing.Usually, cylinder and/or ink roller can be regulated, to increase or to reduce added pressure (being also referred to as " squeegee pressure " at this).
The print speed printing speed of rotogravure can reach and surpass 3000 feet of about per minutes, and applicable to from being lower than 30 centimetres of extremely about 15 feet or above substrate web width.Rotogravure according to the present invention will be added to on-chip printing ink to every kind or layer can comprise a printing machine.Can be added to every layer of printing ink on the substrate, and can make substrate independently intactly come substrate is carried out other processing by printing through separating individually and processor.Yet preferably, device of the present invention comprises the work unit that a plurality of series connection form a line.These work units can comprise one or more following units: substrate launches machine, automatic chip joining machine, the enhancing of substrate surface tension force machine, one or more function and/or figure printing ink machine, slot-cutting machine, location lamination machine, die cutting machine, rewinder and/or inspection machine.
Electrochromic cells of the present invention can constitute like this, and the figure of unit and functional layer are printed onto on single flexible or the rigid substrate.On the other hand, the unit also can constitute like this, only the layer of selecting is printed onto on a slice substrate of selecting in two or the multi-disc flexibility or rigidity substrate, then each single substrate is joined together to form complete electrochromic cells.On-chip these electrochromic cells, figure and other thing combination of elements can be referred to as " passage " separately to be added to each.When during constituting an electrochromic cells, two or more passage being arranged, each passage numeral, for example " first passage ", " second channel " etc.
In a plurality of channel architectures, in case printed each passage, then these several passages are carried out accurate localization each other, and be connected to form a complete unit.Before the present invention, not only effectively the functional part of electrochromic cells is printed onto on the substrate, and makes two or more passage alignment and consistent, make their various layers all have desirable electricity and contact with physics, this is not impossible, but is difficult yet.Therefore, method of the present invention has been introduced a kind of height location laminated device accurately and reliably, and it can carry out with such method, promptly when when the expansion unit is presented out the first passage of preprinting, can print second channel, and after this accurately be laminated on the first passage immediately.
As shown in from above-mentioned discussion, the prescription of every kind of printing ink all is conclusive for reliably and at high speed producing electrochromic cells.If printing ink does not have proper formula, then the layer of each passage is can not be suitably dry, may with other material production chemical reaction, may not adhere on the adjacent layer, also may during handling, cause substrate distortion or fracture.Therefore, constitute necessary these materials of electrochromic cells of the present invention, especially constitute those used materials of functional electrode and dielectric substrate and be printing ink through special formulation, rather than traditional printing ink and non-ink material.
For person skilled in the art, to the detailed explanation of the specific embodiment of the invention, further feature of the present invention, purpose and advantage will become more obvious by with reference to the accompanying drawings.
Summary of drawings
The present invention by shown in following only as an example the description of preferred embodiment will be easier to understand, in the accompanying drawing:
Fig. 1 is the layer exploded view of the electrochromic cells of the layout according to the present invention;
Fig. 2 is the synoptic diagram of the installation method of assembly drawing 1 electrochromic cells;
Fig. 3 is the layer exploded view of another embodiment of the electrochromic cells of layout according to the present invention;
Fig. 4 is the layer exploded view of another embodiment of the electrochromic cells of layout according to the present invention;
Fig. 5 is under assembling condition, the profile of the electrochromic cells of Fig. 4;
Fig. 6 is the view along Fig. 5 VI-VI line;
Fig. 7 is the profile of institute's region in Fig. 5 arrow VII;
Fig. 8 is the synoptic diagram of assembling another embodiment of the apparatus and method of the electrochromic cells of formation according to the present invention;
Fig. 9 is the synoptic diagram of apparatus and method of the electrochromic cells of assembly drawing 3;
Figure 10 is a synoptic diagram of assembling the apparatus and method of two passages that constitute electrochromic cells according to the present invention;
Figure 11 is a synoptic diagram of assembling the apparatus and method of a passage that constitutes electrochromic cells according to the present invention; With
Figure 12 is the planimetric map of some parts of the switching mechanism that can produce with method and apparatus of the present invention.
Embodiments of the present invention
With reference to accompanying drawing, wherein, in institute's drawings attached, identical reference symbol is represented identical or corresponding parts, show first preferred embodiment according to the present invention exploded view of all layer that produce, that comprise electrochromic device in Fig. 1 in schematic form, this unit is represented with reference number 10 usually.Electrochromic cells 10 comprises substrate 12, is printed with electrode material 14, electrolyte 16 and counter electrode material 18 on it.Also can print respectively the connection electrode or terminal 20 and 22 that link with electrode layer 14 and counter electrode 18 electricity.
For example, tin indium oxide material and bismuthino material are used separately as electrode 14 and electrolyte 16, are present in the bismuth ion electron gain in the electrolyte 16, the bismuth metal is then electroplated on electrode 14, cause producing appreciable significant change in electrode 14, that is, tin indium oxide is from the transparent black that changes into.
The part of terminal 20 and 22 not pattern of wants unit 10 as long as such device is provided, that is, can be incorporated into voltage difference on electrode layer 14 and the counter electrode layer 18 by it, makes and produces desirable electrochemical reaction in the unit 10.
The order that selection is used for unit 10 each component materials and assembles these parts is decided by the concrete application of unit 10 to be used to a great extent.For example, the structure of unit 10 shown in Figure 1 illustrates, and substrate 12 contacts with electrode layer 14, and the latter generally is the material that trends towards change state or color during electrochromic reaction, thinks that the observer provides the visual indication of this reaction.Therefore, for the structure of this preferable unit 10, electrode layer 14 is transparent basically when not applying voltage.And substrate 12 preferably also is transparent basically, so that can observe the reaction on the electrode layer 14.
The another kind of structure of unit 10 embodiment shown in Figure 1 comprises counter electrode 18, directly is added on the substrate 12, then, connects dielectric substrate 16 and electrode layer 14 according to the order of sequence.In this improved embodiment, substrate 12 will need not to be transparent basically, because electrode 14 will be not covered by any layer that applies thereafter.
Therefore, method and apparatus of the present invention allows to print each layer with random order, to produce desirable electrochromic reaction.More particularly, the order of printing Fig. 1 embodiment layer can be put upside down, so that print counter electrode 18 earlier on substrate 12, prints electrode 14 then on electrolyte 16, forms unit 10.
Forward the concrete property of printed layers 14,16 and 18 now to, electrode layer 14 can comprise the material of the prescription according to the present invention, and the indication visual to electrochemical reaction can be provided.Say that generally this indication shows with visible variation in electrode layer 14.The layer 14 that plays cathodic process in unit 10 also should be suitable for adhering on substrate 12 and preferably any other layers that may contact with it.
As with all layers of method printing of the present invention, but electrode layer 14 preferably has the characteristic properties of printing-ink.In addition, the printing ink of layer 14 preferably has higher electric conductivity (wishing less than 50 ohm-sq mils), and has and have such as electrochromic reactions such as plating the active ingredient of high-affinity.The same with the many layers with method printing of the present invention, electrode 14 preferably is easy to make any desirable shape and thickness, and rapid draing before unit 10 follow-up all layers apply.
The thickness of electrode layer 14 between 0.05 and 5 mils, preferably, approximately from 0.2 mil to 0.3 mil.As all layers of the printing according to the present invention, electrode layer 14 can be with the individual layer printing, and its thickness can be regulated by the relative concentration of the consistent main prescription composition of this composition scope that changes and the back will be disclosed.On the other hand, the thickness of layer 14 (with other layer of unit 10) can only increase by printing follow-up ink material layer.
Can comprise one of following as the printing ink of electrode layer 14: tin indium oxide (" ITO ") base oil China ink, the bright tinbase printing ink of oxygen, antimony trioxide base oil China ink and the printing ink that has and be mixed with hydrofluoric tin ash.This preferred embodiment plan is used as electrode layer 14 to ITO base oil China ink.Use has the necessary characteristic of desirable chemical reaction in the generation unit 10, but and the prescription that also has an ITO of ink characteristics be considered to unique.At this on the one hand, preferably following being made into of suitable electrode ink of exploitation according to the present invention:
From about 20 to about 80 percentage by weights (wt%), more preferably be about at least a plating agent acceptor of 50wt%;
From about 5 to about 40wt%, more preferably be about the bonding agent of 10wt%;
From about 15 to about 75wt%, more preferably be about the solvent of 40wt%.
Electroplate the agent acceptor wish to be at least a easily with the material of bonding agent and solvent form to produce high conductivity and to produce the non-printing ink that is clamminess that is generally of high quality graphic (coating thickness and covering denseness are even substantially) can be on being added to substrate the time.This material can suitably comprise the conducting powder of above-claimed cpd, preferably comprises the ITO powder.Suitable ITO powder comprises by being essentially that spherical ITO particle is formed and can getting the ITO powder by being essentially the commercialization that aciculiform or rod ITO particle form.The plan of this preferred embodiment makes conducting powder comprise the ITO powder with the aciculiform of being essentially or rod particle between the ITO powder and 0 to 100% that having between 0 to 100% be essentially spheric grain.Special good ITO powder comprises four parts of basic aciculiforms or the rod particle peace treaty portion potpourri of spheric grain basically of having an appointment.But the inventor has been found that this potpourri and has optimized best electrical conductivity that is essentially aciculiform or rod particle and the best substrate spreadability that is essentially spheric grain.
Suitable bonding comprises the resin tissue, and such as Polyvinylchloride, polyvinyl butyral, acrylic acid and nitrocellulose, preferable resin is a vinyl chloride.
And suitable solvent comprises positive propyl acetate, second alcohol and water, and preferable solvent is that positive second is joined propyl ester.
When it was used as electrode 14, the suitable thickness scope of the ITO printing ink of this prescription preferably was about 0.2 mil to 0.3 mil between 0.05 mil to 5 mil.
No matter any electrolyte is solid, semisolid or liquid, all must keep the threshold level of temperature in the electrolyte component, so that electrolyte reaches the effect of its expection.Therefore, preferably electrolyte 16 comprises a kind of wetting agent at least.Wetting agent must have the available service life period in desired unit 10, is enough to absorb and keep the hygroscopic nature of moisture.The wetting agent that is applicable to these purposes can be any in several chlorine, sulphur and the bromine salt, and preferable wetting agent is a lithium bromide.
Electroplate agent and present a kind of at least like this form of material, added under the effect of EMF, it electrochemically combines with the plating agent acceptor material of electrode layer 14, or on " being electroplated onto " this material.This electrochemical reaction can be nonvolatil or reversible according to the plating agent and the plating agent acceptor material of the specified selection of being expected by electrochromic cells 10 of service guide-line.
After the electrochemical reaction appointment of electroplating between agent and the plating agent acceptor, for example be reversible, then electroplating agent should be when when adding suitable EMF, be easy to electroplate and separate out in electroplating on the agent acceptor, and when removing or reverse the EMF polarity chron, be easy to break away from, and turn back to the material of equilibrium state (assistance of following " washing agent " perhaps will be arranged) from electroplating the agent acceptor.
Therefore, electroplate the compound that agent preferably comprises a kind of salt at least, the ion of its formation exists under the suitable counter electrode with adding or remove (or counter-rotating) relative EMF (such as the DC voltage that is about 1.5V) correspondingly separately or combination again.The example of suitable plating agent includes, but are not limited to: WO
3, MoO
3, V
2O
5, Nb
2O
3And BiCl
3(bismuth trichloride).Can be used as the preferred compounds of electroplating agent at present is bismuth trichloride, under the effect of the EMF that applies, its positive charge bismuth ion is removed, and electronegative plating agent acceptor on temporary transient and the electrode layer 14, for example tin indium oxide combination is to produce the visible change that is generally black in electrode layer.Simultaneously, the negative charge chlorion that bismuth trichloride is electroplated agent is removed, and temporary transient and positively charged counter electrode layer 18 combines (below will describe in more detail).
When removing or reverse EMF, electroplate the bismuth ion that discharges positive charge the agent receptive material from the electrode layer of electrode 14, from counter electrode 18, discharge the negative charge chlorion, in electrolyte 16, form bismuth chloride and balance again.In order to promote and accelerate this process, electrolyte 16 can be chosen and preferably further include " washing agent " wantonly.Washing agent should comprise suitable material, salt compound for example, when the cell processing equilibrium state, when promptly not applying EMF, perhaps when the polarity of the EMF that applies when desired electric electrochromic reaction opposite taken place with, its positive ion is electroplated the agent acceptor to the negative charge of electrochromic layer 14 and is had bigger chemical affinity than the positive ion of above-mentioned plating agent.Briefly, when the unit was in equilibrium state, the positive charge ion of washing agent had been replaced the positive charge ion of electroplating agent naturally on the bonding position of the plating agent acceptor of electrode layer 14.
An example that has the washing agent of useful work in electrolyte 16 is chlorination two bronze medals, though also can use other the material that can prove above-mentioned cleaning function.
16 1 preferred embodiments of electrolyte are mixed with two parts of electrolyte compounds, and every part all individually as printable electrolyte printing ink.Yet when making up with the described method of Figure 10, two parts of things are merged into single material, and it has the feature of special electrolyte and structural integrity.
The first of electrolyte composition 16 (hereinafter referred to as " electrolyte A ") rapid draing is near entering into the non-basically state that is clamminess.Therefore, electrolyte A also is applicable to the subsequent treatment in the high-speed printer.For example, in rotogravure, for example, electrolyte A can be easy to receive additional ink lay, comprises function and colour painting printing ink, and does not jeopardize it self, added printing ink after can not influencing or forbid to replace, and, with the electrolyte A printing unit in downstream of can not making dirty.
On the contrary, the moisture content that the second portion of electrolyte 16 (hereinafter referred to as " electrolyte B ") keeps is than electrolyte A height, and keeps some viscosity when depositing on substrate.Therefore, electrolyte B as moisture source, so that contact with each other at two-layer electrolyte, and when two-layer electrolyte layers contacts with electrode layer 14, reaches firm mechanical connection with electrolyte A, and impels electrochemical action simultaneously.Yet, in addition, because its being clamminess property, so electrolyte B is used as last ink lay in the typical multicomputer printing passage of basement membrane, sheet or roll web.
When being implemented as printable printing ink, every kind of electrolyte A and B preferably comprise above-mentioned plating agent and wetting agent, and its weight percent proportioning (wt%) is as follows:
From 0.2 to 1.0wt%, more preferably be about the plating agent of 0.6wt% approximately;
From 0.4 to 10wt%, more preferably be about the wetting agent of 7%wt% approximately.
Two kinds of electrolyte A and electrolyte B should have basic denseness and expected thickness uniformly, and in fact, but also have any desirable pattern being used as on any flexibility or rigidity substrate of printing surface.In the many-side research and development when the present invention finishes, the inventor finds, when selecting with above-mentioned plating agent and wetting agent coupling, some quantity and the combinations produce of solvent and bonding agent go out the electrolyte ink material, it has favourable electrochemical properties, and has usually or electrolyte A or the desirable physical features of electrolyte B.
Therefore, electrolyte A, the quick-drying electrolyte printing ink that is not clamminess basically preferably also comprises:
From 10 to 60wt%, more preferably be about the appropriate organic solvent of 40wt% approximately, it includes, but are not limited to the alcohol such as ethyl, isopropyl, n-pro-pyl or methyl alcohol etc.; Perhaps such as the acetate of ethyl, isopropyl, n-pro-pyl or methyl alcohol etc.; The potpourri of pure and mild acetate, preferable potpourri is 80/20 ethanol/positive acetate third lipoprotein mixture at present; Ketone; Toluene etc.; And
From 2 to 30wt%, preferably be about polyvinyl butyral, Polyvinylchloride, acrylic acid, nitrocellulose and the vinyl chloride copolymer of 8wt% approximately, for example ethyl acrylate acid (EAA)/vinyl chloride is as bonding agent.
And electrolyte B, the electrolyte printing ink that is clamminess preferably also comprises:
From 15 to 50wt%, the water, alcohol (for example, ethyl, isopropyl, n-pro-pyl, methyl, butanols) or the aqueous alcoholic liquid (preferable solution is 80/20 water/aqueous isopropanol) that preferably are about 35wt% are as solvent approximately; And
From 2 to 30wt%, preferably be about one of polysaccharide, nitrocellulose, hydroxy ethyl fiber, acrylic acid, vinyl or vinyl chloride copolymer of 22wt%, approximately as bonding agent.
If desired, the electrolyte composition also can comprise one or more pigment, with before the electrochromic reaction that expection takes place, during and/or afterwards, in electrochromic cells 10, realize at least a desired visual effect.
Can make up the above-mentioned basic and optional component of dielectric substrate 16 and electrode layer 14 with any suitable technology.For example, under the normal pressure and temperature condition, can make up them with above-mentioned quantitative proportion in batch or continuously.
As previously mentioned, counter electrode 18 is electronegative, therefore can be used as anode electrode in unit 10.Counter electrode 18 can comprise electric conductivity is enough to impel unit 10 to carry out any material of desirable electrochemical reaction, and is suitable for adhering on the dielectric substrate 16, preferably, is suitable for adhering to any other layer of the unit 10 that will contact with counter electrode 18.The thickness of counter electrode 18 can preferably be about 0.3 mil to 0.5 mil between 0.05 mil and 5 mils.
The printing ink that can be used as counter electrode 18 comprises the printing ink of carbon back, money base, the Ni-based and conductive material matrix that other is suitable.Be applicable to that carbon back printing ink of the present invention is Acheson Colloids Company of Port Huron, the article No. that Michigan makes is the product of SS24600.When it was painted counter electrode layer 18, the preferred thickness of the carbon back printing ink of this prescription preferably was about 0.4 mil between 0.1 and 1.0 mils.
Fig. 2 shows the simple mechanism and the method for critical piece of the electrochromic cells 10 of assembly drawing 1 in schematic form.Substrate 12 is located by the laminate substrate steady arm in first printing machine 26 24, and there electrode layer 14 is coated onto on the substrate 12.Substrate 12 is located by the steady arm in second printing machine 28 24 then, and therein can being coated onto on the electrode layer 14 corresponding to the electrode material layer 16 of above-mentioned electrolyte A usually.At last, position by the 24 pairs of substrates of steady arm in the 3rd printing machine 30, and there counter electrode layer 18 is coated onto on the dielectric substrate 16.
An additional step as the inventive method can be provided with terminal 20 and 22 selectively, with respectively with electrode layer 14 and counter electrode layer 18. Terminal 20 and 22 can be made by any conductive material.Preferably, terminal 20 and 22 is made up of electrically conductive ink, for example, silver, copper etc., terminal 20 is printed by the same means of other layer in unit 10 with 22.
In Fig. 1 and the described embodiments of the invention of Fig. 2, terminal 20 can be before the layer 14 that prints electrode, simultaneously or print afterwards.Equally, terminal 22 also can be before printing counter electrode 18, simultaneously or print afterwards.
In order to print terminal 20 and 22, can also be added to another printing machine in the embodiments of the invention shown in Figure 2.For example, can be added to the printing machine of printing terminal 20 before or after the printing machine 26.On the other hand, can be printing machine 26 layer 14 and terminal 20 that makes into to print electrode simultaneously basically.Equally, can be added to another printing machine before or after the printing machine 30, with printing terminal 22.On the other hand, can make to print simultaneously basically printing machine 30 into counter electrode layer 18 and terminal 22.
Select as another kind,, preferably substrate 12 is carried out corona treatment usually when before printing on the substrate 12, with surface tension or " dyne " level of raising substrate 12, thus the cohesiveness of enhancing printing-ink and substrate 12.As is known, corona treatment is added to the electric charge of high voltage, low current on the surface of substrate 12.Equally, utilize the known plasma treatment of this technical field and/or other electricity, machinery also can reach similar result with chemical surface tension force enhancement process.
If the dyne level of substrate 12 is too low, then printing-ink will be tending towards bonding in mode heterogeneous, may form the black pearl of non-uniform thickness on the surface of substrate 12.Yet if improve the dyne level of substrate 12, printing ink will be tending towards more all even thickness and more as one man be adhered on the surface of substrate 12.
Can find out significantly that from the remainder and the claim of following this instructions and accompanying drawing each feature of the present invention described herein can be incorporated among any one embodiment that is discussed.For example, if desired, the described embodiments of the invention of Fig. 1 and Fig. 2 can also comprise that another printing machine prints colour painting printing ink.Especially, when substrate 12 was the PVC layer of substantial transparent, it provided splendid mark to accept face.Therefore, can be before the layer 14 that prints electrode, one or more versicolor colour painting printing ink of printing on substrate 12.At substrate 12 and electrode layer 14 all is under the condition of substantial transparent, and colour painting printing ink just can be printed on the electrode layer 14, as long as they do not influence the function of the layer 14 in the unit 10.
And, can be added to a bottom substrate layer 34 (as shown in Figure 3) on the counter electrode layer 18.Substrate layer 34 can provide multiple advantage, for example protects printing surface, provides colour painting to accept face, and/or electrical isolation is provided, and prevents electrochromic cells 10 and ground short circuit.Bottom substrate 34 can be made of any of the material that constitutes substrate 12, comprises, but is not limited to this PVC film, and thickness is between 0.4 and 4 mils.
In addition, can be printed onto each printed layers of unit 10 on whole preceding one deck, on the part that one deck is selected before perhaps can only being printed onto.The shape of each printed layers is commonly referred to " artwork ", and is decided by the shape and the capacity of the image-carrier that is etched into printing cylinder.When the artwork of each layer makes electrochromic cells 10 short circuits (promptly, electrode layer 14 becomes directly and contacts with counter electrode layer 18, thereby electric bypass electrolyte 16) time, can on part (otherwise this place will electrically contact) address of electrode layer 14 and counter electrode layer 18, print a layer insulating, for example print one deck dielectric ink.
(Fig. 3) at least one embodiment of the present invention is provided with dielectric layer 38, avoids the corrosion of electrolyte 16 with protection terminal 22.In the structure of unit 10, electrolyte 16 is acid, and tends to other component layer of seepage and destruction unit 10.Therefore, if carry out suitable setting, dielectric layer can prevent the damage of 16 pairs of unit 10 of electrolyte basically.And if carry out suitable location, dielectric layer can also prevent the short circuit of terminal 20 and 22 pairs of counter electrodes 18.
When dielectric ink was used as insulation course, in order to reach suitable insulation, the gross thickness of single or multiple lift dielectric ink was preferably between 0.3 and 0.4 mil.For example, the two layers of dielectric layer is added on the unit 10, every layer between 0.15 and 0.20 mil.Consider from attractive in appearance and function, also can be arranged to shades of colour to dielectric ink.
And, in some instances, can be figure or other suitable printing ink as the insulation between unit 10 all layers.Some insulation courses not only can provide the electrical isolation between layer and the layer like this, and can prevent to take place between the chemical reaction layer disadvantageous chemical reaction.For example, if bottom substrate 34 comprises metal level, counter electrode 18 comprises carbon back printing ink, then can be added to a layer pattern printing ink between bottom substrate and the counter electrode layer.Add this insulation and played destructive chemical reaction potential between the metal level that prevents counter electrode 18 and substrate 34.
It shall yet further be noted that each layer that comprises unit 10 can also be provided with shades of colour, with function and the requirement attractive in appearance that adapts to the device that comprises unit 10.
Also can be suitable jointing material, for example pressure adhesive is added on arbitrary layer of unit 10, for example is added on the counter electrode 18, forever or temporarily unit 10 is fixed on the flexibility or rigidity surface in addition, unit 10.Bonding coat can apply with the printing unit on the rotogravure or other suitable printing equipment.Can be added to jointing material on the whole surface of unit 10 relevant layers, perhaps apply with predetermined pattern, with the electrical communication between the functional part of avoiding hindering unit 10, and on the shielding cell or element memory any figure.
In Fig. 1 and the described embodiments of the invention of Fig. 2, can be on the printing unit 30 or independently print on the unit on the outside surface that jointing material is added to counter electrode layer 18 for example.When using pressure adhesive, on bonding agent being added to for example counter electrode 18 after, suitable release paper is added on the bonding agent.So the unit 10 of structure can be used as the pressure-sensitive adhesive label effectively.Because the label that obtains has the characteristic of film, therefore in fact can be added to any suitable surface to unit 10, for example device for marking, graphic presentation, commodity demonstration, wrist-watch and dry cell etc.
Because they can be suitable for the application of high speed printing well, can high yield ground productive unit 10 fast, so the rotogravure printing apparatus and method have especially comprised flexible substrate layer 12 when unit 10 to realizing that the present invention is best.And, because each layer of unit 10 can be printed onto (scope of web width is approximately from several inches to several feet) on roll web or the substrate page or leaf 12, so can print a plurality of unit simultaneously according to unit 10 specific sizes.Also can carve the printing cylinder that is included in each printing unit, can print a plurality of unit 10 simultaneously so that printing cylinder whenever turns around.The quantity of the printed unit that whenever turns around is to a great extent with unit 10 with independently the size of printing cylinder is relevant.Use apparatus and method of the present invention, be about at width that to use through being about 7 inchages on 20 inches the web substrate coil paper be 24 inches printing cylinder when producing a plurality of unit 10, web velocity can reach above 100 feet of per minutes.When on web substrate coil paper 12, producing a plurality of unit 10, preferably be coated on the web surfaces opposite, then with suitable release paper covering with printing element 10 with pressure adhesive.Can easily be divided into independent unit 10 to the roll web that includes the unit 10 that assembles by cutting technique then.Therefore, release paper is as the flexibility support and the Storage Media that drape over one's shoulders module units.After so handling, the unit can be retained on the release paper easily, so that manually or for example automatically take off use by automatic labeling device later on.Can peel waste material or the array handled between each printing element 10, then on the recoil unit, recoiling on spool or the roll shaft, so that the roll shaft of finishing is tested, edits, packed and transports by the unit 10 of a volume release paper support.
When also planning in the unit 10 assemblings and after finishing assembling each parts of electrochromic cells 10 are checked.This inspection manually and/or is automatically carried out after can and/or finishing unit 10 during assembling is handled.Can use online or off-line inspection method and technology.
This inspection method and technology can be utilized in this technical field known optics or other automatic check system.Can and use optical vision system during the module units 10 or on any other aspect afterwards in each printing and/or assembling unit, at printing of selecting and/or assembling unit.Can detect in unit 10 arbitrary parts can observable characteristic, for example each printed layers is vertical and/or laterally superimposed, vertical and/or laterally superimposed between each unit 10 during a plurality of unit 10 of printing on the continuous substrate sheet roll web, every layer thickness, (no matter being printing or prefabricated), every layer color, and the sharpness of every layer of printing.
Can also test the electrical property of each parts in the electrochromic cells 10 with online or off-line test process.For example, during assembling process, can test the arbitrary layer of electrochromic cells 10 (such as electrode layer 14, dielectric substrate 16, counter electrode layer 18, terminal 20 and 22 and/or other parts) overall electrical resistance or pressure drop.Test each parts separately and/or cumulatively at assembly process, and result and known permissible range are compared.
If the test indication has parts or a series of parts to surpass acceptable tolerance, then can give the operator of printing machine the signal that indication must be regulated, so that printing machine is carried out manual shift.On the other hand, also can automatically feed back to computerized printer control system to indicator signal, for regulating with the correction problem automatically.If have parts or a series of parts to surpass acceptable tolerance, then also can be manually or automatically close printing machine.
Fig. 3 shows the exploded view according to the another embodiment of 10 all layers of further embodiment of this invention institute productive units.Unit 10 can be used to indicate the relative pressure drop on the terminal 20 and 22.Fig. 3 also shows method of the present invention can use the multi-form of the printed artwork of how many kinds of.
The embodiment of the unit 10 shown in Fig. 3 can use at needs and quantitatively indicate in any application of relative pressure drop on the terminal 20 and 22.For example, can detect the charged state such as EMF32 such as dry cell (Fig. 1), wherein the electrode of EMF32 contacts with 22 with terminal 20.
When being connected on terminal 20 and 22 such as EMF32 sources such as dry cells, the electrode layer 14 that is positioned on the voltage divider 36 with the form of single section carries out electrochemical reaction with the form of change color.For the configuration of the artwork of Fig. 3, the voltage that changes existence on hop count and terminal 20 and 22 of electrode layer 14 of color is directly proportional.In other words, the hop count that changes color is many more, and the voltage that then is present on terminal 20 and 22 is just high more.Therefore, voltage is high more, and the quantity of the section 14 of change color is many more, then illustrates in the just tested dry cell to remain with higher electric charge.
The unit 10 of present embodiment comprises substrate 12, is printed with like this some layers thereon, electrode material 14, comprises the voltage divider 36 of terminal 20 and 22 and insulative dielectric material 38.Preferably, substrate 12 comprises the PVC film, and electrode layer 14 comprises ITO printing ink, and voltage divider 36 comprises traditional silver-colored printing ink, and insulation course 38 comprises dielectric ink.
Can also in the embodiment of unit 10, select to include bottom substrate 34.Substrate 34 can comprise any material of describing with previous embodiment.Yet in the present embodiment, substrate 34 preferably comprises one deck PVC layer at least, also can comprise some figure ink laies and/or vacuum deposited metal layer, for example aluminium.
In one embodiment, substrate 34 can comprise the layer of aluminum vacuum deposited layer and be adhesively fixed on non-contraction PVC film on this aluminium lamination on the collapsible PVC film of one deck.Can be added to one deck pressure adhesive on the collapsible PVC surface relative with the vacuum moulding machine aluminium lamination.Pressure adhesive can be adhered to desirable surface to unit 10, for example indicates the surface of demonstration, dry cell or wrist-watch.Preferably, can increase one deck release paper, cover pressure adhesive.
According to the special applications of unit 10 expections, substrate 34 can have multiple other structure.For example, PVC can be applicable to that the membraneous material by rotogravure replaces with other.These materials can comprise other plastic material, paper, sheet metal, metal forming and, complex etc. can ink deposition or other material on it.
Forward the concrete property of the printed layers of unit shown in Figure 3 10 now to, the material that electrode 14, electrolyte 16, counter electrode 18, dielectric 38 can component units 10, its thickness is basically as mentioned above.
As mentioned above, in order suitably to play the effect of any electrochromic cells, its electrolyte part can not only impel between itself and negative electrode and anode and produces desirable electrochemical reaction, but also must prevent the short circuit between the electrode.Back one requires making the particular importance that seems in the application according to electrochromic cells 10 of the present invention with one or more flexible substrates (for example layer 12 and 34), and especially (it is according to a preferred embodiment of the present invention at least) is all the more so when dielectric substrate 16 is viscoelasticity basically in its service life process.Thereby, in manufacturing, transportation, loading and unloading with between the operating period, be generally gel and viscoelastic dielectric substrate 16 and may stand significant local contraction power, this will cause that dielectric substrate is compressed to makes electrode layer 14 and counter electrode layer 18 contacted stage, thereby cause electrochromic cells 10 short circuits, and perhaps also can cause irreversible infringement.
Therefore, the present invention has also designed a device 100 that stops compression electrolyte layers 16.According to the present invention, to shown in Figure 7, this device can separate with electrolyte layers, and/or in aggregates with electrolyte layers as Fig. 4.
Now forward Fig. 4 and Fig. 5 to, electrochromic cells 10 comprises substrate 12, electrode layer 14, dielectric substrate 16 and counter electrode layer 18, and discuss in conjunction with Fig. 1 and Fig. 3 their composition and thickness and front, and their homologue is consistent.Therefore, will be not described in detail the further details of these parts, and only describe its structure, composition and/or function and the visibly different feature of they above-mentioned homologues, perhaps for understanding the necessary content of the present invention.
Perhaps in Fig. 7, can be clear that, in its simplest form, stop the device 100 of compression dielectric substrate 16 to constitute by the device that is incorporated in most of electrolyte itself, and by reduce externally it flows and ability of compressing improves the structural strength of dielectric substrate under the afterburning influence.This device can comprise any suitable diffusing dead-wood material (force distributing material), for example fiber and/or special material.The good material of a kind of spy is multiple minimized spherical basically particle, here abbreviate " spheroid " 102 as, it is (as shown in the figure) or with other special material and/or can combine or use with the fibrous material of electrolyte 16 combination and deposition separately.Spheroid 102 can be solid or hollow (as shown in the figure).They can pass through the known method of this technical field, and (for example glass maybe can form the minimum spheroid that is not less than about 50 μ m (more preferably less than about 20 μ m, goodly less than about 10 μ m) and makes by the material of rigidity basically.Be used for suitable spheroid of the present invention and comprise the hollow glass body, it is by Potter Industries, Inc.of Parsippany, and New Jersey makes.For guarantee that spheroid evenly distributes in whole electrolyte array material when it deposits, preferably before depositing, the electrolyte 16 of spheroid 102 and the preparation according to the present invention (illustration is above-mentioned separate one of matter A and electrolyte B or both) is made up and mix.
Because their shape attitude is spherical in shape substantially, and this shape intrinsic special stressed distribution and transmission characteristic, so spheroid 102 provide stoped unit 10 normally make, transportation, loading and unloading and the collision that may run into when using and the splendid means of other mechanical shock.And, because their normally level and smooth and circular outward appearances, can make viscoelastic electrolyte wrap spheroid 102 with continuous basically array, thus in the unit 10 duration of works, spheroid can not cause material hinder to electroplate agent ion (or washing agent ion) migration.
On the other hand, perhaps except the prevention compression set is incorporated into the dielectric substrate 16, stop the device 100 of compression dielectric substrate can also comprise the material 104 of one deck compression resistance force at least, it be arranged on dielectric substrate 16 and electrode layer 14 and counter electrode layer 18 both one of between or between dielectric substrate 16 and the two.For the purpose of simplifying the description and discuss, only be described in detail in the situation that is arranged on the such one deck 104 between electrode layer 14 and the electrolyte 16 shown in Fig. 4-7 below.Should be appreciated that this structure can be arranged between dielectric substrate 16 and the counter electrode layer applicable to arbitrary layer equally, or dielectric substrate and insertion therebetween any layer and the compression resistance force material layer between electrode and/or the counter electrode layer.
According to preferred embodiment, layer 104 preferably comprises one deck at least such as the covering layer material that can print with recoverable dielectric ink one class, and it can be with any is being added on the electrode layer 14 before dielectric substrate 16 in above-mentioned printing equipment or the method.On the other hand, also can cambium layer 104, be added on the electrode layer 14 before the dielectric substrate 16 then.Layer 104 preferable thickness are from 0.5 to 1.0 mil approximately, so that the section minimum of unit 10, and the resistance characteristics of disturbed zone 104 not.
And, in order to improve the structural strength of layer 104, this one deck can comprise that also auxiliary compression strenght improves material, such as fibrous material, special material or a plurality of size, shape attitude and function and the identical spheroid 108 (Fig. 7) of spheroid 102 in also being incorporated into electrolyte 16, or any combination of these materials.
Fig. 8 shows the apparatus and method of assembly drawing 3 electrochromic cells in schematic form.Should be appreciated that and to assemble this similar unit that principle that other electrochromic cells 10 described herein can be lectured according to the present invention constitutes with similar apparatus and method.The preferred approach of each layer being assembled and appended to substrate 12 is printing.And when coming module units 10 with printing, best typography is to carry out in rotogravure.
At first, position with the 24 pairs of substrates 12 of steady arm in the corona treatment group 40, the dyne level of corona treatment body substrate 12 increases.Though corona treatment is a step preferable in the method for the present invention,, it is not that production functional unit 10 is necessary.
Position with the 24 pairs of substrates 12 of steady arm at least one electrode printing machine 26 then, and in 26, electrode layer 14 is appended on the substrate 12.Then position with at least one voltage divider printing machine 42 interior 24 pairs of substrate 12 of steady arm, and in 42 depressor 36 on the line bonus so that carry out electrical communication with electrode layer 14, and unit 10 just will carry out work as mentioned above.In voltage divider 36 and dielectric material 38, suitable openings 36a and 38a are set, so that dielectric substrate 16 is got in touch with electrode section 14.
Electrochromic cells structure like this, as shown in Figure 3 just can be seen a kind of device that can quantitatively determine EMF voltage as.On the contrary, as do not have the voltage divider such as voltage divider 36 of appointment, the embodiment of unit 10 then shown in Figure 1 (and similar cellular construction) can be generalized into can provide qualitative to the EMF voltage that is applied.For example, different with scale type scale, electrode layer 14 can print like this, and the EMF that applies with box lunch surpasses or when being lower than predetermined threshold, shows to become simple information such as " good " or " replacement " etc.
Then position by the 24 pairs of substrates 12 of steady arm at least one dielectric printing machine 44, and 44 in affix dielectric 38 so that electrochromism section 14 and voltage divider 36 are insulated, to prevent and counter electrode layer 18 short circuits.As mentioned above, an opening 38a is set in dielectric 38, it aligns with the opening 36a of voltage divider 36 usually, so that allow dielectric substrate 16 and electrochromism section 14 to carry out electrical communication.One second opening or otch 38b also are set on dielectric 38, carry out electrical communication, and do not make counter electrode 18 and electrode section 14 short circuits with 36b of branch and the counter electrode 18 that allows voltage divider 36.
Then, by the steady arm at least one electrolyte printing machine 28 substrate 12 is positioned, and in 28, pass through the opening 36a and the 38a of alignment, at least one deck dielectric substrate 16 is appended on the electrode section 14, and do not contact with voltage divider layer 36.At last, position by the 24 pairs of substrates 12 of steady arm at least one counter electrode printing machine 30, and in 30 affix counter electrode layer 18 so that carry out electrical communication with dielectric substrate 16 and voltage divider 36, and not with 14 short circuits of electrochromism section.
Then, as shown in Figure 9, substrate 12 can selectively be positioned in the bottom substrate layer applicator 46, and can be applied to bottom substrate 34 on the unit 10 therein, preferably is applied on the counter electrode 18.In at least one embodiment of the present invention, parts 14,36,38,16 and 18 are wrapped between stacked substrate 12 and the bottom substrate 34, pass applicator 46 simultaneously.Substrate 34 also can be in applicator 46 be applied on the unit 10 by any means that are suitable for substrate 34 is fixed to unit 10, and does not influence the function or the aesthetic of unit 10.That this technique for fixing can comprise is stacked, pressure-sensitive adhesive etc.
Alignment stacked laminator 50 can comprise bottom substrate 34 is fixed to any means on the unit 10 that is printed on the stacked substrate 12.For example, as long as reach the function and the purpose attractive in appearance of unit 10, can use bonding stacked, the heat-sealing or other fixing means.
To selecting to carry out additional treatment step of several steps on bottom substrate steady arm 54 and the bottom substrate 34 of aliging between the stacked laminator 50.For example can by with the corona treatment of stacked substrate 12 in used identical method bottom substrate 34 is carried out corona treatment.Also can be in groover 56 punching press or cut out opening on substrate 34, to produce for example switching mechanism of exciting unit 10.In addition, also can recoil unit and inspection, packing and the transportation function finished to online or off-line is added in the method and apparatus of Fig. 9 embodiment.
Figure 10 shows the embodiment of two passages of the present invention.This embodiment can produce the unit 10 of any suitable purposes, but preferably, can be this label that is configured to constitute the dry cell that comprises unit 10, and when unit 10 is energized, the charged state of pilot cell.
The first passage of present embodiment shown in Figure 10 is schematically illustrated as zone 70." first passage " is the treatment channel that substrate 12 is handled.The treating apparatus that constitutes first passage 70 comprises stacked substrate steady arm 24, corona treatment 40, optional colour painting printing ink unit 58, at least one electrode printing machine 26, at least one dividing potential drop printing machine 42 and at least one dielectric printing machine 44 usually.
Second channel embodiment illustrated in fig. 10 is schematically illustrated as zone 80, " second channel " is the treatment channel of treatment substrate 34.The treating apparatus that constitutes second channel 80 comprises bottom substrate steady arm 54, corona treatment 40, at least one dielectric ink printing machine 60, at least one counter electrode printing machine 30, slot-cutting machine 56 usually, supplies at least one electrolyte printing machine 28 of for example above-mentioned electrolyte A of printing.Can also select to be provided with a stacked bonding printing machine 62, immediately following then can be at least one electrolyte printing machine 28 thereafter, with for example above-mentioned electrolyte B of printing.
In order to merge first and second passages 70 and 80, first passage 70 is fed to alignment stacked laminator 50, arrange, align with second channel 80 and stacked.In device 50, passage 70 and 80 is bonded together as a composite structure.The composite structure that comprises passage 70 and 80 preferably carries out additional treatments in bicker 63, rewinder 64, inspection and montage unit 66 and packing and transporter 68.
First and second passages 70 and 80 can be assembled simultaneously or separately.When printing simultaneously, first and second passages 70 and 80 print in parallel basically rotogravure or similar printing machine, in alignment stacked laminator 50, arrange printing passage 70, and accurately align, fixedly become a composite structure then with second channel 80.And, though do not illustrate, but be to be understood that, comprise be clamminess and two or more channel architectures of the non-electrolyte that is clamminess (such as electrolyte A and B) in, can be one of electrolyte, for example electrolyte A is applied on the substrate, and another electrolyte, for example electrolyte B is applied on another substrate.After this, all substrates are being alignd when stacked, the relation that can contact face-to-face forms the dielectric substrate of combination, thereby makes printed substrate produce functional electrochromic cells in conjunction with electrolyte.
When independent printing, the general first cascade of printing earlier substrate passage 70, but and the storage form placement of further handling after being suitable for roll shaft or other.When wanting stacked, the roll shaft that comprises first passage 70 is installed to the not shown infeed unit that goes out in the stacked laminator 50 that aligns.When printing second channel 80, first passage 70 is launched, arranges, and align with the second channel 80 that installs on 50.Then passage 70 and 80 fixed to one another and location, so that optionally further be processed into a synthetic substrate on the unit 63,64,66 and 68.
In two or more channel architectures, successful structure to unit 10 it is essential, is so to align and is connected single passage together, so that each functional part of unit 10 carries out suitable electrical communication each other, and, produce desirable visual effect the alignment of the graph layer of unit 10.For this reason, preferably on alignment stacked laminator 50 by automatically and continuously self-regulation alignment and lamination process the intact so alignment of each passage and connect together.
In the structure of two passages of above-mentioned battery testing label, usually that first passage 70 is flexible a little once, with adaptive second channel 80.Under the situation of a plurality of unit 10 of printing on the roll web, the repeat patterns of first passage electrochromic cells parts is built into length lacks than the repeat patterns of corresponding units in the second channel 80 slightly.Difference between first and second passages repeat can need only the flexible of first passage 70 and will not cause substrate 12 fractures greatly to the degree that printed layers allowed of first passage.For example, when waiting to incorporate into the electrochromic cells of the cell tester in being fixed to battery label, the difference of repetition is about 0.01 inch usually in printing.Therefore, first passage 70 must be by repeat flexible about 0.01 inch at every turn, so that it can be consistent with the corresponding repetition of second channel 80, to form unit 10.
Alignment according to the present invention is stacked can be realized by cooperation automatic reel paper registration control device (not shown) and the time use appropriate configuration of aliging stacked laminator 50 co-ordinations and the automatic reel paper force control device (not shown) of cooperating, to produce the electrochromic device of two or more passages.A kind of typical structure can comprise that model is that roll web alignment control device and the model of S-3000 is the web tension control device of S-2152, and these two devices all are The Bobst Group, Inc.of Roseland, and New Jersey makes.A kind of like this system can be used for launching from the infeed unit on the stacked device that aligns at first passage 70, and when when second channel withdraws from rotogravure, combining with second channel, control preprinted first passage.On the other hand, can processed offline align stackedly, two passages 70 in there and 80 all print in advance and recoil.
Automatically the crucial part of alignment lamination process is the stress characteristics at each passage of production period watch-keeping.In case unsuitable stress may cause that the passage 70 and 80 that combines takes place to break away from or curl on the first passage 70.For example when assembling electrochromic battery testing label, the tension force size that is placed on the first passage 70 should preferably be about 1.0pli between every linear inch (pli) material about 0.5 pound and about 1pli.
In order to reach real-time basically precision control, the stacked laminator 50 that preferably aligns also comprises roll web orientation sensing device (not shown), their some physical property when aliging stacked laminator 50 to detect first and second passages process.This roll web sensing device preferably is electrically connected on the suitable system control equipment, microprocessor (not shown) for example, it monitors the roll web sensing device continuously, and controls web tension control device and roll web alignment control device simultaneously according to the roll web position data that receives from the roll web sensing device.Web tension control device and roll web alignment control device go for controlling one of first and second passages 70,80 or both relative tension and alignment.
Get back to the treatment step of two passage embodiment of the present invention shown in Figure 10 now, first passage 70 constitutes by following steps: locate the substrate 12 that is in the corona treatment unit 40 for the first time by steady arm 24, and carry out corona treatment there, improve the dyne level of substrate 12.Then, substrate 12 is positioned in one or more available colour painting ink printer 58, applies colour painting printing ink.The printing ink that is coated with can be identical or different color.Colour painting printing ink also can apply in printing machine 58, to provide insulation between each layer of unit 10.
So substrate 12 is positioned at least one electrode printing machine 26, and then is positioned on aforesaid at least one dividing potential drop printing machine 42.Then, substrate 12 is positioned at least one dielectric printing machine 44, applies insulative dielectric printing ink 38.Thickness in the dielectric that applies on the dielectric printing machine 44 can preferably be about 1.0 mils between about 0.2 and 1.5 mils.So far, finished first passage 70, and as mentioned above, but the person can make it to be wound up on the roll shaft so that alignment stacked laminator 50 is perhaps delivered in its aftertreatment.After this, substrate 12 receives one or more electrolyte coatings, for example electrolyte A coating at least one electrolyte printing machine 28.
Then as mentioned above, substrate 34 is positioned at least one counter electrode printing machine 30.Then, substrate 34 is positioned in the grooving unit 56, on printed substrate 34, opening is set by rotating speeder die-cut or that other is suitable.After this, substrate 34 is positioned at least one electrolyte printing machine 28, with the coated electrolyte material, electrolyte A for example.Can be positioned at substrate 34 on the available bonding printing machine then, apply one deck lamination adhesive.Preferably, only bonding agent be coated on the substrate 34 those in alignment stacked laminator 50 first and second passages 70 and 80 necessary zones stacked together on.Also promptly, bonding agent must be printed as and make it not influence the function or the aesthetic of unit 10, and for example, it should not be printed on the place of electrolyte 16.At last, substrate 34 is sent at least one other electrolyte printing machine 28, and can apply one or more layers electrolyte therein, preferably comprise last one deck electrolyte B.
Usually, can on one or more layers of electrochromic device, form opening according to any means of the inventive method.For example, when in above-mentioned cell tester, forming switching device, as described in Figure 12,, the printed substrate 34 of second channel is cut out switch touch groove or opening 48 with groover 56.Can use such as die-cut any cutter sweep that waits, preferably use die-cut technology in the rotational line.The shape of Figure 12 split shed 48 only is for such as the ability of the size of required opening, cutting hatch method, the position of opening and the factors such as desired function of device are preferable shapes with respect to each layer of electrochromic device.Yet should be noted that does not need opening for the effect of unit 10.That is, utilizable uncommon number of openings is decided according to the desired feature of specific electrochromic device and the function that constitute.
The switch contact opening 48 of Figure 12 is arranged to make the terminal 20 of voltage divider 36 to contact with the positive electrode or the negative electrode of the dry cell that is fixed with unit 10 with 22.By the layer in the under shed 48 (being generally the layer of first passage 70) operating switch, like this, terminal 20 contacts with the electrode of dry cell with 22.Yet the crucial part of switching manipulation is and will the layer of unit 10 be suitably alignd and arrange, so that terminal 20 and 22 can carry out electrical communication with battery terminal.Here the present invention who discloses by research and realization will be appreciated that except opening 48, grooving is handled 56 and also had other purposes.
Figure 11 shows another embodiment of the present invention.In this embodiment, only on stacked substrate 12 printing element 10 all the layer.As the embodiment of Figure 10, by stacked substrate steady arm 24 substrate 12 is positioned in the corona treatment 40, subsequently by at least one available colour painting ink printer 58, at least one electrode printing machine 26, at least one dividing potential drop printing machine 42 and dielectric printing machine 44.
Yet, different with the recoil printed substrate 12 in the aforementioned first passage 70, replace a substrate 12 directly by electrolyte printing machine (group) 28, counter electrode printing machine (group 30) and pattern bonded machine 62.Basically with the 12 printing whiles of substrate, bottom substrate 34 is positioned in the corona treatment unit 40, in grooving unit 56, carries out grooving, in alignment stacked laminator 50, accurately align with stacked then with printed substrate 12 by bottom substrate steady arm 54.
In bicker 63, unitized construction is die-cut into each unit 10 then.The advantage of present embodiment be printed substrate 12 with non-coated substrates 34 between whether align no longer with multi-channel structure in the same key that becomes, this is because ink lay needn't be aimed at, to satisfy tolerance.Then unit 10 is recoiled on rewinder 64, checked packing, transportation respectively on unit 66,68, all these processes can be manually or automatically to handle.
It shall yet further be noted that in the embodiment of expection each printing machine (except that the electrolyte printing machine that deposits the electrolyte B printing ink that is clamminess) can comprise the ink setting device, and printed web is passed through this ink setting device after having applied each printed layers.Preferably evaporate organic solvent and/or water in every layer of printing ink, bubble, help its each layer of back to deposit in high quality to prevent ink lay.The dry printing ink that uses among the present invention is relevant with this Several Factors with the method for solvent, for example, impose on the component of pressure, the printing ink of printing ink, before one deck is printed onto under handle on one deck before this printing ink or solvent needed drying time etc.When it when the exsiccator, may be heated drying time and/or air flows through the influence of printing ink.In most of the cases, importantly before applying the layer of back, evaporate the water in the printing ink.Though this problem is main relevant with water-based inks, also is quite tangible for solvent-based ink, it has better drying property than water-based inks usually, but also may contain water in solution, perhaps introduces dewfall in printing process.
Under the situation of rotogravure, allow the time of dry ink lay to increase along with the increase of web length between the printing unit.As usual, the exsiccator of each printing machine is arranged on this printing machine will increases this length.Exsiccator comprises a series of adjustable roll shafts or dancer rools, and roll web is by these rollers.Roll web has been increased the distance of roll web between the printing cylinder by dancer rools.Dancer rools can constitute makes this distance reach desirable any length.
In addition, exsiccator can contain heating element (preferably being infrared element) and hair-dryer, and it improves or reduce the air mixed flow in the exsiccator.The infrared ray heating element is preferable, and this is because infrared ray can both work well to water base or solvent-based ink.And the air that mixed flow is blown into can cool off better and be dry.
Obviously, the appropriate combination of dry variablees such as distance, time, air temperature and current can in very large range change with the printing ink that uses among the desired result.
Should understand, aforesaid content is only in order to illustrate various products, material, apparatus and method, all these helps the present invention, thereby, can be printed onto reliable electrochromic cells fast and at low cost on the flexibility or rigidity substrate, to produce these different devices (but being not limited to these), such as graphic presentation, watch displays and cell voltage or state-of-charge indicator.
The present invention can implement with other concrete form and not break away from its spirit or essential attributes.Therefore, should point out scope of the present invention with reference to appending claims rather than above-mentioned explanation.
Claims (138)
1, a kind of method of making electrochromic cells is characterized in that, comprises the following step:
Printing one deck electrode material on first substrate;
Printing one deck electrolyte on described electrode layer; And
Printing one deck counter electrode material on described dielectric substrate is so that during the introducing voltage difference, produce electrochemical reaction in described electrochromic cells between described electrode layer and described counter electrode layer.
2, the method for claim 1 is characterized in that, described electrode, electrolyte and counter electrode material comprise printing-ink.
3, method as claimed in claim 2 is characterized in that, described electrode ink comprises tin indium oxide base oil China ink.
4, method as claimed in claim 2 is characterized in that, described electrolyte printing ink comprises the bismuth alkali ink.
5, method as claimed in claim 2 is characterized in that, described counter electrode printing ink comprises carbon back printing ink.
6, method as claimed in claim 2 is characterized in that, the thickness of described electrode ink is between 0.5 to 5 mil.
7, method as claimed in claim 2 is characterized in that, the thickness of described electrolyte printing ink is between 0.05 and 50 mils.
8, method as claimed in claim 2 is characterized in that, the thickness of described counter electrode printing ink is between 0.05 and 5 mils.
9, method as claimed in claim 2 is characterized in that, described electrolyte printing ink comprises two parts composition, and the first in the described composition is dried to the state that is not clamminess substantially, and the second portion of described prescription is dried to the state of being clamminess.
10, the method for claim 1 is characterized in that, further comprises second substrate is adhered to step on the described counter electrode layer.
11, method as claimed in claim 10 is characterized in that, described first substrate comprises polychloroethylene film.
12, method as claimed in claim 10 is characterized in that, described second substrate comprises polychloroethylene film.
13, method as claimed in claim 12 is characterized in that, the thickness of described first substrate is between 0.4 and 4 mils.
14, method as claimed in claim 12 is characterized in that, the thickness of described second substrate is between 0.4 and 4 mils.
15, method as claimed in claim 10, it is characterized in that, also comprise the following step: accept to print at least on the face one deck colour painting printing ink at the mark of described unit, described mark is subjected to bread to contain the described colour painting printing ink that described first substrate, described second substrate, described electrode material, described counter electrode material and one deck deposit in advance.
16, method as claimed in claim 10 is characterized in that, also is included in the step that improves the described first substrate surface tension force before being printed onto on described first substrate.
17, method as claimed in claim 15 is characterized in that, also is included in the step that improves the described second substrate surface tension force before being printed onto on described second substrate.
18, the method for claim 1 is characterized in that, also comprises the step that printing and described electrode layer carry out the first terminal of electrical communication.
19, method as claimed in claim 18 is characterized in that, also comprises the step that printing and described counter electrode layer carry out second terminal of electrical communication.
20, method as claimed in claim 19 is characterized in that, described first and second electrodes comprise voltage divider.
21, method as claimed in claim 20 is characterized in that, described first voltage divider prints with silver-based inks.
22, the method for claim 1 is characterized in that, also is included between described electrode layer and the described counter electrode layer to print one deck dielectric material at least.
23, method as claimed in claim 10 is characterized in that, also comprises the step of stacked described first and second substrates.
24, method as claimed in claim 23 is characterized in that, also be included in described first and second substrates stacked before, another step of aliging in one of described first and second substrates and described first and second substrates.
25, method as claimed in claim 24 is characterized in that, also is included in stacked described first and second substrates step of the figuratum lamination adhesive of printing on one of described first and second substrates before.
26, the method for claim 1 is characterized in that, also comprises the step that forms an opening at least on one of described first and second substrates.
27, a kind of label is characterized in that, includes the electrochromic cells of making according to the method for claim 1.
28, a kind of charged state test component is used to test dry cell, it is characterized in that, according to the method manufacturing of claim 1.
29, a kind of visual display spare is characterized in that, according to the method manufacturing of claim 1.
30, a kind of device for marking is characterized in that, according to the method manufacturing of claim 1.
31, a kind of timer is characterized in that, according to the method manufacturing of claim 1,
32, the method for claim 1 is characterized in that, described these layers of printing in single passage.
33, the method for claim 1 is characterized in that, described these layers of printing in surpassing one passage.
34, the method for claim 1 is characterized in that, described these layers of printing in two passages.
35, the method for claim 1 is characterized in that, by described these layers of rotogravure printing.
36, the method for claim 1 is characterized in that, makes a plurality of electrochromic cells on a web substrate coil paper basically simultaneously.
37, method as claimed in claim 36 is characterized in that, all individual units described electrochromic cells optionally take off from described roll web.
38, a kind of method of making electrochromic cells is characterized in that, comprises the following step:
Printing one deck electrode material on first substrate;
Printing comprises the layer of described first electrolyte on described electrode layer;
Printing one deck counter electrode material on second substrate;
Printing comprises the layer of the described electrolyte of second portion on described counter electrode material; And
Link described first and second substrates,, thereby make first and second substrates of described binding produce functional electrochromic cells so that the described first and the second portion of described first electrolyte contact with each other.
39, method as claimed in claim 38 is characterized in that, the component of the described first of described electrolyte is different with the described component of the described second portion of described electrolyte.
40, method as claimed in claim 38, it is characterized in that, one of described first and second parts of described electrolyte are dried to the state that is not clamminess substantially, and another is dried to the state of being clamminess in described first and second parts of described electrolyte.
41, a kind of device of making electrochromic cells is characterized in that, described device comprises:
The device of printing one deck electrode material on first substrate;
The device of printing one deck electrolyte on described electrode layer; And
The device of printing one deck counter electrode material on described dielectric substrate is so that during the introducing voltage difference, produce electrode reaction on described electrochromic cells between described electrode layer and described counter electrode layer.
42, device as claimed in claim 41 is characterized in that, described electrode, electrolyte and counter electrode material comprise printing-ink.
43, device as claimed in claim 42 is characterized in that, described electrode ink comprises tin indium oxide base oil China ink.
44, device as claimed in claim 42 is characterized in that, described electrolyte printing ink comprises the bismuth alkali ink.
45, device as claimed in claim 42 is characterized in that, described counter electrode printing ink comprises carbon back printing ink.
46, device as claimed in claim 42 is characterized in that, the thickness of described electrode ink is between 0.05 to 5 mil.
47, device as claimed in claim 42 is characterized in that, the thickness of described electrolyte printing ink is between 0.05 and 50 mils.
48, device as claimed in claim 42 is characterized in that, the thickness of described counter electrode printing ink is between 0.05 and 5 mils.
49, device as claimed in claim 41 is characterized in that, also comprises second substrate is bonded to device on the described counter electrode layer.
50, device as claimed in claim 49 is characterized in that, described first substrate comprises polychloroethylene film.
51, device as claimed in claim 50 is characterized in that, described second substrate comprises polychloroethylene film.
52, device as claimed in claim 49, it is characterized in that, the mark that also is included in described unit accepts to print at least on the face device of one deck colour painting printing ink, and described mark is accepted the described colour painting ink lay that bread contains described first substrate, described second substrate, described electrode material, described electrolyte, described counter electrode material and deposited in the past.
53, device as claimed in claim 52 is characterized in that, also is included in the device that described first substrate of printing improves the described first substrate surface tension force before.
54, device as claimed in claim 52 is characterized in that, also is included in the device that described second substrate of printing improves the described second substrate surface tension force before.
55, device as claimed in claim 41 is characterized in that, also comprises the device that prints the first terminal, to carry out electrical communication with described dielectric substrate.
56, as device as described in the claim 55, it is characterized in that, also comprise the device that prints second terminal, to carry out electrical communication with described counter electrode layer.
57, device as claimed in claim 56 is characterized in that, described first and second electrodes comprise voltage divider.
58, device as claimed in claim 57 is characterized in that, described voltage divider is arranged between described electrode layer and the described counter electrode layer.
59, device as claimed in claim 58 is characterized in that, described voltage divider comprises silver-based inks.
60, device as claimed in claim 41 is characterized in that, also is included in the device that prints one deck dielectric material between described electrode layer and the described counter electrode layer at least.
61, device as claimed in claim 49 is characterized in that, also comprises the device of stacked described first and second substrates.
62, device as claimed in claim 61 is characterized in that, also be included in described first and second substrates stacked before, another device that aligns in one of described first and second substrates and described first and second substrates.
63, device as claimed in claim 62 is characterized in that, also is included in stacked described first and second substrates device of the figuratum lamination adhesive of printing on one of described first and second substrates before.
64, the described method of claim 41 is characterized in that, also comprises the device that forms an opening at least on described first substrate.
65, device as claimed in claim 41 is characterized in that, described electrochromic cells forms the pressure-sensitive adhesive label.
66, device as claimed in claim 41 is characterized in that, described electrochromic cells forms the test component of the charged state of test dry cell.
67, device as claimed in claim 41 is characterized in that, described electrochromic cells forms visible display device.
68, device as claimed in claim 41 is characterized in that, described electrochromic cells forms the sign display.
69, device as claimed in claim 41 is characterized in that, described electrochromic cells forms timer.
70, device as claimed in claim 41 is characterized in that, each described printing equipment is arranged to make described device printshop in single passage that described layer is arranged.
71, device as claimed in claim 41 is characterized in that, each described printing equipment is arranged to make described device printshop in surpassing a passage that described layer is arranged.
72, device as claimed in claim 41 is characterized in that, each described printing equipment is arranged to make described device printshop in two passages that described layer is arranged.
73, device as claimed in claim 41 is characterized in that, prints each described layer by rotogravure.
74, device as claimed in claim 41 is characterized in that, makes a plurality of electrochromic cells on a web substrate coil paper basically simultaneously.
75, as the described device of claim 74, it is characterized in that, all individual unit selectivity in the described electrochromic cells are taken off from described roll web.
As the described device of claim 73, it is characterized in that 76, described rotogravure comprises the chemical etching printing cylinder.
77, a kind of printable electrode ink that is used for electrochromic cells is characterized in that, described electrochromism printing ink comprises:
Electroplate the agent acceptor;
Solvent; And
Bonding agent.
As the described electrode ink of claim 77, it is characterized in that 78, described plating agent acceptor is from following selection: tin indium oxide, tin oxide, three tin oxide and be mixed with hydrofluoric tin oxide.
As the described electrode ink of claim 77, it is characterized in that 79, described solvent is from following selection: positive propyl acetate, second alcohol and water.
As the described electrode ink of claim 77, it is characterized in that 80, described bonding agent is from following selection: Polyvinylchloride, polyvinyl butyral, acrylic acid and nitrocellulose.
81, as the described electrode ink of claim 77, it is characterized in that, the quantity of described plating agent acceptor is from about 20 to 80 percentage by weights, and the quantity of described solvent is from about 15 to 75 percentage by weights, and the quantity of described bonding agent is from about 5 to 40 percentage by weights.
82, a kind of electrochromic cells is characterized in that, comprises the electrode ink of claim 77.
83, a kind of printable electrolyte printing ink that is used for electrochromic cells is characterized in that described electrolyte printing ink comprises:
Electroplate agent;
Wetting agent;
Solvent; And
Bonding agent.
As the described electrolyte printing ink of claim 83, it is characterized in that 84, described plating agent is from following selection: WO
3, MoO
3, V
2O
5, Nb
2O
3And BiCl
3
As the described electrolyte printing ink of claim 84, it is characterized in that 85, described plating agent is BiCl
3
As the described electrolyte printing ink of claim 84, it is characterized in that 86, described plating agent comprises the described printing ink of from 0.2 to 1.0 percentage by weight approximately.
As the described electrolyte printing ink of claim 83, it is characterized in that 87, described wetting agent is a lithium bromide.
As the described electrolyte printing ink of claim 87, it is characterized in that 88, described wetting agent comprises the described electrolyte printing ink of from 4 to 10 percentage by weights approximately.
As the described electrolyte printing ink of claim 83, it is characterized in that 89, described solvent is from following selection: potpourri, ketone and the toluene of alcohol, acetate, alcohol and acetate.
As the described electrolyte printing ink of claim 89, it is characterized in that 90, described alcohol is from following selection: ethyl, isopropyl, n-pro-pyl and methylol, described acetate are from following selection: ethyl, isopropyl, n-pro-pyl and methylol; And the potpourri of described alcohol and acetate is the potpourri of ethanol and positive propyl acetate.
As the described electrolyte printing ink of claim 90, it is characterized in that 91, described solvent is the potpourri of ethanol and positive propyl acetate.
As the described electrolyte printing ink of claim 89, it is characterized in that 92, described solvent comprises the described electrolyte printing ink of from 10 to 60 percentage by weights approximately.
As the described electrolyte printing ink of claim 89, it is characterized in that 93, described bonding agent is from following selection: polyvinyl butyral, Polyvinylchloride, acrylic acid, nitrocellulose and vinyl chloride copolymer.
As the described electrolyte printing ink of claim 93, it is characterized in that 94, described bonding agent is a polyvinyl butyral.
As the described electrolyte printing ink of claim 93, it is characterized in that 95, described bonding agent comprises the described electrolyte printing ink of from 2 to 30 percentage by weights approximately.
As the described electrolyte printing ink of claim 83, it is characterized in that 96, described solvent is from following selection: water, pure and mild aqueous alcohol solutions.
As the described electrolyte printing ink of claim 96, it is characterized in that 97, described solvent is water and aqueous isopropanol.
As the described electrolyte printing ink of claim 96, it is characterized in that 98, described solvent comprises the described electrolyte printing ink of from 15 to 50 percentage by weights approximately.
As the described electrolyte printing ink of claim 96, it is characterized in that 99, described bonding agent is from following selection: polysaccharide, nitrocellulose, hydroxy ethyl fiber, acrylic acid, vinyl or vinyl chloride copolymer.
As the described electrolyte printing ink of claim 99, it is characterized in that 100, described bonding agent is a polysaccharide.
As the described electrolyte printing ink of claim 99, it is characterized in that 101, described bonding agent comprises the described electrolyte printing ink of from 2 to 30 percentage by weights approximately.
102, as the described electrolyte printing ink of claim 83, it is characterized in that, also comprise wetting agent.
As the described electrolyte printing ink of claim 102, it is characterized in that 103, described wetting agent is chlorination two bronze medals.
104, as the described electrolyte printing ink of claim 83, it is characterized in that, also comprise at least one pigment.
105, as the described electrolyte printing ink of claim 83, it is characterized in that, when also being included in described electrolyte printing ink and being configured to parts of electrochromic cells, stop the device of described electrolyte printing ink compression.
As the described electrolyte printing ink of claim 105, it is characterized in that 106, the device of described prevention compression comprises a plurality of spheroids.
As the described electrolyte printing ink of claim 106, it is characterized in that 107, described spheroid is made by the material of rigidity basically.
As the described electrolyte printing ink of claim 106, it is characterized in that 108, the diameter of described spheroid is less than about 50 μ m.
109, a kind of electrochromic cells is characterized in that, comprises right and wants 83 electrolyte printing ink.
110, a kind of electrolyte prescription is characterized in that, comprises:
First comprises:
As the bismuth trichloride of electroplating agent;
Lithium bromide as wetting agent;
Ethanol and positive propyl acetate as solvent; And as the polyvinyl butyral of bonding agent; And
Second portion comprises:
As the bismuth trichloride of electroplating agent;
Lithium bromide as wetting agent;
Water and aqueous isopropanol as solvent; And as the polysaccharide of bonding agent.
111, a kind of electrolyte is characterized in that, comprises second electrolyte that is essentially non-first electrolyte that is clamminess and is clamminess.
112, a kind of electrochromic cells is characterized in that, comprises:
Anode;
Negative electrode;
Be arranged on the electrolyte between described anode and the negative electrode; And
Compress described electrolytical device by the prevention of described electrolyte supported.
As the described electrochromic cells of claim 112, it is characterized in that 113, described electrolyte is viscoelastic basically.
As the described electrochromic cells of claim 112, it is characterized in that 114, the device of described prevention compression comprises a plurality of spheroids that are incorporated in the described electrolyte.
As the described electrochromic cells of claim 114, it is characterized in that 115, described spheroid is made by the material of rigidity basically.
As the described electrochromic cells of claim 114, it is characterized in that 116, the diameter of described spheroid is less than about 50 μ m.
117, a kind of electrochromic cells is characterized in that, comprises:
Anode;
Negative electrode;
Be arranged on the electrolyte between described anode and the negative electrode; And
Be arranged in described electrolyte and described anode and the negative electrode prevention between at least one and compress described electrolytical device.
As the described electrochromic cells of claim 117, it is characterized in that 118, described electrolyte is viscoelastic basically.
As the described electrochromic cells of claim 117, it is characterized in that 119, the device of described prevention compression comprises the material of one deck compression resistance force at least.
120, as the described electrochromic cells of claim 119, it is characterized in that, but described compression resistance force material comprises printing-ink.
As the described electrochromic cells of claim 119, it is characterized in that 121, described compression resistance force material is configured to the discontinuous structure that is limited by at least one clearance space, to receive described electrolyte.
As the described electrochromic material of claim 119, it is characterized in that 122, described compression resistance force material comprises auxiliary compression strenght reinforcing material.
As the described electrochromic material of claim 122, it is characterized in that 123, described auxiliary compression strenght reinforcing material comprises a plurality of spheroids that are incorporated in the described compression resistance force material.
As the described electrochromic cells of claim 123, it is characterized in that 124, described spheroid is made by the material of rigidity basically.
As the described electrochromic cells of claim 123, it is characterized in that 125, the diameter of described spheroid is less than about 50 μ m.
126, a kind of method of making electron device is characterized in that, described method comprises the following step:
(a) but print first substrate surface with first printing-ink, produce first parts of electron device;
(b) but print second substrate surface with second printing-ink, produce second parts of electron device; And
(c) the described print surface of described first and second substrates, connect face-to-face, make described first and second parts produce the function electron device.
As the described method of claim 126, it is characterized in that 127, described first and second substrates are made with described flexible material.
As the described method of claim 126, it is characterized in that 128, described electron device is an electrochromism battery testing device.
129, as the described method of claim 126, it is characterized in that, also be included in and carry out print steps (a) and print steps (b) in the high-speed printer.
130,, it is characterized in that described high-speed printer is a rotogravure as the described method of claim 129.
131, as the described method of claim 126, it is characterized in that, step (c) comprises makes described the one the second substrates pass through stacked laminator simultaneously, monitor simultaneously at least a characteristic of at least one substrate in described first and second substrates continuously, under described supervision, another substrate alignment in a substrate in described first and second substrates and described first and second substrates, and agent is merged described first and second substrates by wish.
132, a kind of device of making electron device is characterized in that, described device comprises:
But the surface of printing first substrate with first printing-ink is with the device of first parts that produce electron device;
But print second substrate surface with second printing-ink, with the device of second parts that produce electron device; And
The described print surface of described first and second substrates, connect face-to-face, make described first and second parts produce the device of function electron device.
As the described device of claim 132, it is characterized in that 133, described first and second substrates are made with described flexible material.
As the described device of claim 132, it is characterized in that 134, described electron device is an electrochromism battery testing device.
135, as the described device of claim 132, it is characterized in that, also be included in the device that prints the device of first substrate in the high-speed printer and print second substrate).
136,, it is characterized in that described high-speed printer is a rotogravure as the described device of claim 135.
As the described device of claim 132, it is characterized in that 137, the device of the described printing surface of described connection comprises the device of stacked described first and second substrates.
138, as the described device of claim 137, it is characterized in that, when described stacked laminator is included in described substrate by described stacked laminator, basically monitor the device of at least one characteristic of at least one substrate in described first and second substrates continuously and in response to described supervision, the device of another substrate alignment in a substrate and described first and second substrates in described first and second substrates, and the device that merges described first and second substrates by wish alignment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97191559 CN1207182A (en) | 1996-10-01 | 1997-10-01 | Apparatus and method for assembling electrochromic cells |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/724,349 | 1996-10-01 | ||
| CN 97191559 CN1207182A (en) | 1996-10-01 | 1997-10-01 | Apparatus and method for assembling electrochromic cells |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA021557837A Division CN1515949A (en) | 1996-10-01 | 1997-10-01 | Device and method for assembling electrochromism unit |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1207182A true CN1207182A (en) | 1999-02-03 |
Family
ID=5179027
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97191559 Pending CN1207182A (en) | 1996-10-01 | 1997-10-01 | Apparatus and method for assembling electrochromic cells |
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| CN (1) | CN1207182A (en) |
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1997
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