CN102455560A - Electrochromic module and stereoscopic imaging display device with same - Google Patents

Abstract

The present invention provides an electrochromic module and a stereoscopic imaging display device having the module, wherein the electrochromic module comprises a first substrate, a second substrate, at least one electrochromic layer and at least one ion layer. At least one first conductive element is provided on the upper surface of the first substrate. The electrochromic layer is provided between the first substrate and the second substrate. The ion layer is provided on the surface of the electrochromic layer, and the material thereof is made by mixing an organic material and an inorganic material dissolved in a solvent. The ion layer can not only act as an ion provider, but also is a kind of electrochromic material itself, and can be used as an auxiliary color-changing layer to increase the difference in optical transmittance. By transferring and transmitting electrons between organic and inorganic materials, the color change speed is faster and more uniform, and has the advantages of a smaller driving voltage.

Description

Electrochromic module and stereoscopic imaging display device with the module

technical field

The present invention is an electrochromic module and a stereoscopic imaging display device with the module, relating to an electrochromic module that uses electrochromic material as an ion layer to provide ions to the electrochromic layer and a stereoscopic imaging display with the module A device, especially an ion layer material, is made by mixing an organic material and an inorganic material in a solvent.

Background technique

Electrochromism (EC for short) material means that under the action of current or electric field, the electrochromism material undergoes light absorption or light scattering, resulting in a reversible change in color.

Please refer to FIG. 1 , which is a schematic diagram of an electrochromic module in the prior art. As shown in the figure, the electrochromic module 1 includes: a first substrate 11 , a second substrate 12 , an electrochromic layer 13 and an electrolyte layer 14 . A first conductive element 111 is disposed on the upper surface of the first substrate 11 , and a second conductive element 121 is disposed on the lower surface of the second substrate 12 . Electrons are provided through the first conductive element 111 and/or the second conductive element 121 and ions are provided to the electrochromic layer 13 through the electrolyte layer 14 , so that the ions enter the crystal lattice to cause a discoloration effect. Or as shown in FIG. 2 , FIG. 2 is a schematic diagram of another electrochromic module in the prior art. On the structure of the electrochromic module in FIG. 1, on the electrolyte layer 14, another reversed electrochromic layer 15 is provided as an ion storage layer and an auxiliary color-changing layer. The effect opposite to that of the electrochromic layer 13 is used to increase the difference in optical transmittance.

The electrochromic module of the existing structure, its materials are all made of transition element oxides or hydroxides or their derivatives into inorganic solid films or mixed with organic compounds/electrolyte materials to form composite materials, which provide additional ions through electrons Sources (such as electrolytes or second electrochromic materials) allow ions to enter the lattice to cause discoloration, such as WO3, Ni(OH)2, Prussian blue, etc.

The materials of the existing electrolyte layer can be roughly divided into solid electrolyte, liquid electrolyte and gel electrolyte. However, the above-mentioned electrolyte materials only have the function of providing ions to the electrochromic layer. If it is desired to increase the difference in optical transmittance, an additional electrochromic layer 15 is required as shown in FIG. 2 . Therefore, it will cause the thickness of the electrochromic module 1 to increase, which is not conducive to the further application of the electrochromic module 1 , which is really a pity.

The principle of general stereoscopic image display technology is to utilize binocular disparity (Binocular disparity) to receive different images through the left and right eyes respectively, and finally fuse them into a stereoscopic image in the brain. In naked-eye stereoscopic display technology, it can be roughly divided into two types according to its structure: lenticular and barrier. Electrochromic materials are used to achieve the barrier, and it has the ability to switch to display stereoscopic images or flat surfaces. Stereoscopic image display device for images, related patents such as:

Patent Publication of Taiwan Province of China, Announcement No. M368088 "Integrated Electrochromic 2D/3D Display", Announcement No. M371902 "Display Device for Switching 2D Planar Image/3D Stereoscopic Image Display Screen", Announcement No. I296723 "Color Filters for Liquid Crystal Panels Capable of Stereoscopic Images and Manufacturing Method Thereof" and U.S. Patent Publication No. 2006087499 "Autostereoscopic 3D display device and fabrication method thereof", etc. The chromic material is used as a parallax barrier device for displaying stereoscopic images, but the common defect in the structure of M368088 and M371902 is that they lack the necessary electrolyte layer for the electrochromic device. Because of the lack of an electrolyte layer that can provide ions to the electrochromic layer, The electrochromic device will not be able to produce a reversible reaction of oxidation or reduction to complete the coloring or decolorization change, so these patents should not be implemented in practice; in addition, the transparent electrode layer and the electrochromic material layer of the parallax barrier device are set as Fence patterns, layered coating, sputtering or etching in the manufacturing process, and even each stack must be accurately aligned, the process is quite complicated, and all stacks are set as a fence pattern, resulting in a gap between each fence and the fence. The formation of a hollow area will affect the overall light penetration, refraction or reflection, even for general 2D display, it may also affect the image quality of the display, causing problems such as color difference or uneven brightness; and I296723 is embedded in a liquid crystal display and molded in The structure of the color filter, and the electrochromic layers in all the above-mentioned patents use existing electrochromic materials and color-changing mechanisms, which require a large driving voltage, which is likely to cause material defects and short service life.

Therefore, how to invent an electrochromic module that can increase the difference in optical transmittance without increasing the thickness of the electrochromic module, so that it can be used more widely, and how to apply these electrochromic modules in The stereoscopic imaging display device will be actively disclosed by the present invention.

Contents of the invention

In view of the shortcomings of the above-mentioned electrochromic module, the inventor felt that it was not perfect, so he exhausted his mind to study and overcome it, and developed an electrochromic module based on his accumulated experience in this industry for many years, with a view to The purpose of simplifying the manufacturing process and increasing the difference in optical transmittance is achieved without increasing the thickness.

An object of the present invention is to provide an electrochromic module in which an ion layer made of an organic material and an inorganic material dissolved in a solvent serves as an electrolyte layer and an auxiliary electrochromic layer.

An object of the present invention is to provide an electrochromic module with fast coloring/fading, high cycle life and low driving voltage.

An object of the present invention is to provide an electrochromic module capable of deepening the color of the electrochromic material.

To achieve the above purpose, the electrochromic module of the present invention includes: a first substrate with at least one first conductive element on its upper surface; a second substrate; at least one electrochromic layer arranged on the first Between a base plate and the second base plate; and at least one ion layer, which is arranged on the surface of the electrochromic layer, and its material is made by mixing an organic material and an inorganic material in a solvent.

And the structure of the electrochromic module of the present invention can have many different implementation modes:

1. When the first conductive element, the electrochromic layer and the ionic layer are multiple, each of the first conductive elements is respectively arranged in the form of an accommodating tank to accommodate the electrochromic layer and the ionic layer .

2. When the first conductive element, the electrochromic layer and the ion layer are multiple, there are more barrier units arranged between the first conductive element, the electrochromic layer and the plasma layer between.

3. When the first conductive element and the electrochromic layer are multiple, the first conductive elements are alternately provided with positive and negative voltages, and the electrochromic layers are respectively arranged in the form of an accommodating groove to accommodate the tape The first conductive elements are negatively charged.

4. When the first conductive element and the electrochromic layer are multiple, the first conductive elements alternately provide positive and negative voltages, and the electrochromic layers are respectively arranged on the negatively charged first conductive elements superior.

The electrochromic layer and the ion layer are colored/discolored by applying different positive and negative voltages through the first conductive element.

Furthermore, the electrochromic module of the present invention may further have at least one second conductive element disposed on the lower surface of the second substrate. And the second conductive element can also be arranged in the above-mentioned four-point structure, as follows:

1. When the first conductive element, the second conductive element, the electrochromic layer and the ion layer are multiple, each of the first conductive element and the second conductive element is respectively arranged in the form of an accommodating tank, To accommodate the electrochromic layer and the ion layer.

2. When the first conductive element, the second conductive element, the electrochromic layer and the ion layer are multiple, there are more barrier units, which are arranged on the first conductive element, the second conductive between the element, the electrochromic layers and the plasma layer.

3. When the first conductive element and the electrochromic layer are multiple, the first conductive elements alternately provide positive and negative voltages, the second conductive element provides positive voltage, and the electrochromic layers are respectively arranged as a The accommodating groove is in the form of accommodating the negatively charged first conductive elements.

4. When the first conductive element and the electrochromic layer are multiple, the first conductive elements alternately provide positive and negative voltages, the second conductive element provides positive voltage, and the electrochromic layers are respectively arranged on On the negatively charged first conductive elements.

Giving different positive and negative voltages to the first conductive element and the second conductive element can speed up the coloring/fading of the electrochromic layer and the ionic layer, and can limit the discoloration range of the electrochromic layer and the ionic layer .

Another object of the present invention is to provide a stereoscopic imaging display device using the electrochromic module, which has the function of switching the display state of 2D images and 3D images.

To achieve the above purpose, the stereoscopic imaging display device of the present invention includes: an image display module for displaying a plane image and a stereoscopic image; and the electrochromic module mentioned above.

If the electrochromic module is viewed microscopically, a plurality of electrochromic modules can be respectively used as gratings and arranged in the display device. Or if viewed as a whole, an electrochromic module with a plurality of electrochromic layers needs to be used as a grating and arranged in the display device to achieve the shielding function.

Thereby, the electrochromic module and the stereoscopic imaging display device of the present invention have a difference that can improve the optical transmittance without increasing the thickness of the electrochromic module and the stereoscopic imaging display device, fast coloring/fading, and high cycle life And the driving voltage is small.

Description of drawings

FIG. 1 is a schematic diagram of an electrochromic module in the prior art.

FIG. 2 is a schematic diagram of another prior art electrochromic module.

FIG. 3 is a schematic diagram of an electrochromic module according to a first embodiment of the present invention.

Fig. 4 is a schematic diagram of an electrochromic module in which the first conductive element is arranged in multiple aspects according to the second embodiment of the present invention.

FIG. 5 is a schematic diagram of an electrochromic module in which electrochromic layers are arranged in multiple aspects according to a third embodiment of the present invention.

6 to 10 are schematic diagrams of an electrochromic module in which the first conductive element and the electrochromic layer are arranged in multiple ways according to the fourth embodiment of the present invention.

11 is a schematic diagram of an electrochromic module in which the first conductive element is arranged in a plurality of accommodating slots according to a fifth embodiment of the present invention.

FIG. 12 is a perspective view of the electrochromic module of FIG. 11 .

FIG. 13 is a schematic diagram of an electrochromic module in which the first conductive element is arranged in multiple aspects as a barrier according to the sixth embodiment of the present invention.

FIG. 14 is a top view of the electrochromic module of FIG. 13 .

FIG. 15 is a perspective view of the electrochromic module of FIG. 13 .

16 is a schematic diagram of an electrochromic module in which a first conductive element, an electrochromic layer, and an ion layer are arranged in multiple configurations and a barrier unit is provided therebetween according to a seventh embodiment of the present invention.

FIG. 17 is a schematic diagram of an electrochromic layer arranged in multiple forms and serving as an electrode according to an eighth embodiment of the present invention.

18 is a schematic diagram of an electrochromic module further provided with a second conductive element according to a ninth embodiment of the present invention.

FIG. 19 is a schematic diagram of an electrochromic module further provided with a second conductive element under the second substrate of FIG. 9 according to the tenth embodiment of the present invention.

FIG. 20 is a schematic diagram of an electrochromic module further provided with a second conductive element under the second substrate of FIG. 10 according to an eleventh embodiment of the present invention.

FIG. 21 is a schematic diagram of an electrochromic module in which the first conductive element and the second conductive element are arranged in multiple configurations and sequentially serve as a barrier according to the twelfth embodiment of the present invention.

FIG. 22 is a top view of the electrochromic module of FIG. 21 .

FIG. 23 is a perspective view of the electrochromic module of FIG. 21 .

Fig. 24 is a schematic diagram of an electrochromic module with two stacked electrochromic layers according to the thirteenth embodiment of the present invention.

Fig. 25 is a schematic diagram of an electrochromic module provided with three stacked electrochromic layers according to the fourteenth embodiment of the present invention.

FIG. 26 is a schematic diagram of an electrochromic module according to a thirteenth embodiment of the present invention combined with a design aspect of the sixth embodiment of the present invention.

27 is a schematic diagram of an electrochromic module according to the fourteenth embodiment of the present invention combined with the design aspect of the sixth embodiment of the present invention.

28 is a schematic diagram of a stereoscopic imaging display device in which a plurality of electrochromic modules are arranged in one image display module according to a fifteenth embodiment of the present invention.

FIG. 29 is a schematic diagram of a stereoscopic imaging display device in which the electrochromic module of FIG. 16 is provided in an image display module according to a sixteenth embodiment of the present invention.

Explanation of reference signs:

1-electrochromic module; 11-first substrate; 111-first conductive element; 12-second substrate; 121-second conductive element; 13-electrochromic layer; 14-electrolyte layer; 15-auxiliary color-changing layer ; 2-electrochromic module; 21-first substrate; 211-first conductive element; 22-second substrate; 221-second conductive element; 23-electrochromic layer; Electrochromic layer; 24-ion layer; 25-barrier unit; 3-image display module.

Detailed ways

In order to enable your examiners to clearly understand the content of the present invention, the following descriptions are provided together with the drawings, please refer to them.

First, please refer to FIG. 3 , which is a schematic diagram of an electrochromic module according to a first embodiment of the present invention. Wherein, the electrochromic module 2 includes a first substrate 21 , a second substrate 22 , an electrochromic layer 23 and an ion layer 24 . A first conductive element 211 is disposed on the upper surface of the first substrate 21 . The electrochromic layer 23 is disposed between the first substrate 21 and the second substrate 22 . The ion layer 24 is arranged on the surface of the electrochromic layer 23 and grounded, and its material is made by mixing an organic material and an inorganic material in a solvent.

Therefore, when a positive voltage or a negative voltage is applied to the first conductive element 211 to generate a voltage difference, the first conductive element 211 can extract or provide electrons to the electrochromic layer 23, and through the ion layer 24 With the provided ions, the electrochromic layer 23 produces an oxidation or reduction reaction to complete the color removal or coloring change. And the ionic layer 24 itself is also an electrochromic material made by dissolving an organic material and an inorganic material in a solvent and has the characteristics of oxidation and reduction reactions, so it also produces oxidation while losing or gaining electrons. or reduction reaction to produce decolorization or coloring changes with the electrochromic layer 23 . In addition, by controlling the solution concentration, potential difference, solvent polarity, pH value, pole distance, and dielectric constant of the ion layer 24, the difference in optical transmittance of the ion layer 24 can be increased or decreased. .

In addition, the electrochromic module 2 of the present invention can be implemented in different structural forms, please refer to FIG. 4 to FIG. 23 .

Fig. 4 is a schematic diagram of an electrochromic module in which the first conductive element is arranged in multiple aspects according to the second embodiment of the present invention. As shown in the figure, the first conductive element 211 is arranged in a plurality of forms, so that the electrochromic layer 23 and the ion layer can be adjusted as each first conductive element 211 is respectively given positive and negative voltages. 24 The coloring/decoloring effect and speed of each block make the electrochromic module 2 have further application.

FIG. 5 is a schematic diagram of an electrochromic module in which electrochromic layers are arranged in multiple aspects according to a third embodiment of the present invention. As shown in the figure, the ion layer 24 is also grounded to generate a voltage difference, so the first conductive element 211 can extract or provide electrons to the electrochromic layer 23, and by the ions provided by the ion layer 24, the The electrochromic layer 23 produces oxidation or reduction reaction to complete the change of decolorization or coloring. And by arranging the electrochromic layer 23 in multiple forms, it can be used as a grating, so as to be used in a stereoscopic imaging display device.

6 to 10 are schematic diagrams of an electrochromic module in which the first conductive element and the electrochromic layer are arranged in multiple ways according to the fourth embodiment of the present invention. As shown in the figure, by arranging the first conductive element 211 and the electrochromic layer 23 in multiple ways, each first conductive element 211 can be provided with positive and negative voltages according to different requirements (as shown in FIG. 9 , shown in Figure 10), to adjust the coloring/decoloring effect and speed of each block of the electrochromic layer 23 and the ion layer 24 corresponding to each position, and then adjust the interval between the formed gratings, and can be applied to There are various settings for generating moiré images for image encoding, or for adapting to various process methods.

11 is a schematic diagram of an electrochromic module in which the first conductive element is arranged in a plurality of accommodating slots according to a fifth embodiment of the present invention. FIG. 12 is a perspective view of the electrochromic module of FIG. 11 . As shown in the figure, the first conductive element 211, the electrochromic layer 23 and the ion layer 24 are all arranged in multiple forms, and since the ion layer 24 exists in the form of a solution, the first conductive element 211 can be respectively It is arranged in the form of an accommodating tank to store the ion layer 24 so that it will not overflow.

FIG. 13 is a schematic diagram of an electrochromic module in which the first conductive element is arranged in multiple aspects as a barrier according to the sixth embodiment of the present invention. FIG. 14 is a top view of the electrochromic module of FIG. 13 . FIG. 15 is a perspective view of the electrochromic module of FIG. 13 . As shown in the figure, the first conductive element 211, the electrochromic layer 23 and the ion layer 24 are all arranged in multiple forms, and since the ion layer 24 exists in the form of a solution, the first conductive element 211 can be respectively It is provided as a barrier to store the ion layer 24 so that it will not spill. The first conductive element 211 respectively provides positive and negative voltages sequentially to generate a voltage difference to extract or provide electrons.

16 is a schematic diagram of an electrochromic module in which a first conductive element, an electrochromic layer, and an ion layer are arranged in multiple configurations and a barrier unit is provided therebetween according to a seventh embodiment of the present invention. As shown in the figure, since the ionic layer 24 exists in the form of a solution, when the ionic layer 24 is arranged in multiple forms, a barrier unit 25 is further provided between them, as a barrier, to store the plasma layer 24 so that Will not spill. The barrier unit 25 is made of photoresist. In this embodiment, the ion layer 24 is also grounded, and the first conductive element 211 provides positive and negative voltages to generate a voltage difference to extract or provide electrons.

Fig. 17 is according to the eighth embodiment of the present invention, the first substrate 21 is provided with at least one first conductive element 211, the first conductive element 211 only provides positive voltage, and the electrochromic layer 23 is polymorphic Different from the above-mentioned embodiments, the electrochromic layers 23 also have the function of electrodes, and here, the electrochromic layers 23 are given a negative voltage. If it is this kind of implementation, the selected The electrochromic material itself must have conductive polymers with conductive and color-changing functions, such as polyaniline.

The electrochromic module of the present invention can further have at least one second conductive element disposed on the lower surface of the second substrate. The second conductive element can be provided in the electrochromic modules in FIGS. 3 to 16 in single or multiple forms, thereby generating a potential difference. Therefore, in these embodiments, the ion layer does not need to be grounded. Since other structures are the same, they will not be repeated here, and several implementation modes of such aspects are listed below for reference.

18 is a schematic diagram of an electrochromic module further provided with a second conductive element according to a ninth embodiment of the present invention. As shown in the figure, the electrochromic module 1 of the present invention can further have at least one second conductive element 221 disposed on the lower surface of the second substrate 22 . The second conductive element 221 is provided in a single form here. By arranging the second conductive element 221 on the other side, the first conductive element 211 and the second conductive element 221 can accelerate the rate of providing or withdrawing electrons, and The coloring/fade rate of the electrochromic layer 23 and the ion layer 24 can be increased.

FIG. 19 is a schematic diagram of an electrochromic module further provided with a second conductive element under the second substrate of FIG. 9 according to the tenth embodiment of the present invention. FIG. 20 is a schematic diagram of an electrochromic module further provided with a second conductive element under the second substrate of FIG. 10 according to an eleventh embodiment of the present invention. The second conductive element 221 is provided in a single form here, and the positive and negative voltages are provided alternately by the first conductive elements 211, and the second conductive element 221 provides a positive voltage, so that electrons can be pulled by the positive voltage and move to The activity range of the electrons is limited, thereby limiting the coloring/fading range of the ion layer 24 .

FIG. 21 is a schematic diagram of an electrochromic module in which the first conductive element and the second conductive element are arranged in multiple configurations and sequentially serve as a barrier according to the twelfth embodiment of the present invention. Fig. 22 is a top view of the electrochromic module of Fig. 21. Fig. 23 is a perspective view of the electrochromic module of Fig. 21. As shown in the figure, similar to Figure 13, Figure 13 only uses the first conductive element 211 as a barrier, but in this embodiment, the first conductive element 211 and the second conductive element 221 can be arranged alternately between the plasma layer 24 to prevent its overflow.

The concept of the above-mentioned embodiments is to block the phenomenon of cross talk caused by the discoloration of the isolation sublayer 24 by controlling the electric field; a preferred embodiment in the above-mentioned embodiments is an interdigitated electrode, such as the first conductive element 211 Alternately arranged with the second conductive element 221 and provided with positive and negative electrodes respectively, the position of the ion layer 24 when changing color can be effectively limited to the negative electrode of the second conductive element 221 .

As for the components of the above-mentioned electrochromic module 2, including the first substrate 21, the first conductive element 211, the second substrate 22, the second conductive element 221, the electrochromic layer 23 and the ion layer 24 The material will be described together below.

The material of the first substrate 21 and the second substrate 22 is plastic, polymer plastic, glass or is selected from resin, polyethylene terephthalate (Polyethylene Terephthalate, PET), polycarbonate (Poly Carbonate, PC ), polyethylene (Polyethylene, PE), polyvinyl chloride (Poly VinylChloride, PVC), polypropylene (Poly Propylene, PP) and polystyrene (Poly Styrene, PS) and polymethylmethacrylate (Polymethylmethacrylate, PMMA) One of the group of plastic polymers.

The material of the first conductive element 211 and the second conductive element 221 is selected from indium tin oxide (Indium Tin Oxide, ITO), indium zinc oxide (Indium Zinc Oxide, IZO), zinc aluminum oxide (Al-doped ZnO, AZO ) and antimony tin oxide (Antimony Tin Oxide, ATO) composed of one of the group of mixed oxides (Impurity-Doped Oxides) or carbon nanotubes (carbonnanotube), poly-3,4-ethylene dioxide Conductive polymer materials such as thiophene PEDOT (Poly-3,4-Ethylenedioxythiophene).

The electrochromic layer 23 is an organic electrochromic material, an inorganic electrochromic material, a transition metal oxide, a transition metal compound, or a composite material of a transition metal compound and an organic electrochromic material, and its setting method can be as follows Preparation: such as sol-gel method, sputtering method, plating method, screen printing, spray coating, anodizing method, photopolymerization method, laser etching method , electrophoresis or electrochemical synthesis deposition, etc.

The organic electrochromic material is bipyridyls, viologen, anthraquinone, tetrathiafulvalene or pyrazolone redox compounds and their derivatives; Or Polyacetylene, Polyaniline, Polypyrrole, Polythiophene, Poly-3-alkylthiophene, Polyfuran, Polyphenylene sulfide (Polyphenylene), aromatic polyamide/polyimide or polyphenylenevinylene (Polyphenylenevinylene) conductive polymers and their derivatives; or polymetallic complexes and their derivatives; or coordination of transition metals and lanthanides bit complex and its derivatives; or metal phthalocyanine and its derivatives; or ferrocene (Ferrocene), iron thiocyanate [iron (III) thiocyanate] dissolved in aqueous solution, hexacyanoferric The acid salt is dissolved in tetracyanoquinone or tetrathiocyanide in acetonitrile.

The transition metal oxide is selected from chromium oxide (Cr ₂ O ₃ ), nickel oxide (NiO _x ), iridium oxide (IrO ₂ ), manganese oxide (MnO ₂ ), nickel hydroxide Ni(OH) ₂ and dioxypentoxide One of the anodic coloration (anodic coloration) transition metal oxide groups composed of tantalum (Ta ₂ O ₅ ); or selected from tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ), niobium oxide (Nb ₂ O ₃ ), titanium oxide (TiO ₂ ), strontium titanate (SrTiO ₃ ) and tantalum pentoxide (Ta ₂ O ₅ ) are one of the cathodic coloration transition metal oxides. or be selected from vanadium oxide (V ₂ O ₂ ), rhodium oxide (Rh ₂ O ₃ ) and cobalt oxide (CoO _x ) in the transition metal oxide group of cathodic/anodic coloration (cathodic/anodic coloration) one.

The transition metal compound is Prussian blue (Fe ₄ [Fe(CN) ₆ ] ₃ ).

The inorganic electrochromic material is a C60 film doped with Li, K, Mg, Cr, Cu and Ba.

The organic material of the ion layer 24 is a redox indicator or a pH indicator (acid-base indicator). Redox indicator (Redox Indicator) is an indicator used in redox titration, which can produce obvious color changes at a specific electrode potential. It is generally an organic reagent with redox properties itself. Its oxidized and reduced forms Available in different colors, there are two common types of redox indicators: metal-organic complexes, organic redox systems, etc. Almost all redox indicators and organic redox systems involve protons (i.e. H+) as participants in electrochemical reactions, so according to this characteristic, redox indicators can also be divided into two types: pH-dependent redox indicators , and a pH-independent redox indicator. pH-independent redox indicators include: 2,2'-bipyridyl ruthenium complex ion, 5-nitrophenanthrite complex ion, N-phenylanthranilic acid, 1,10-o-diazepine complex ion Ferrous complex ion, wool poppy red, paraquat, 2,2'-bipyridyl ferrous complex ion, 5,6-dimethyl-o-phenanthrin complex ion, 3,3'-dimethoxy Benzidine, sodium diphenylamine sulfonate, N,N'-diphenylbenzidine, diphenylamine, viologen, etc., but some indicators are toxic; and pH-dependent redox indicators include: dichlorophenol indophenol Sodium, sodium o-cresol indo, thionine, methylene blue, indigo tetrasulfonic acid, indigo trisulfonic acid, indigo carmine, indigo monosulfonic acid, phenol safranin, safranin T, neutral red, etc. pH indicator (acid-base indicator) is a chemical reagent used to test the pH value. It is a weak acid or base and contains a pigment. When it is dropped into the solution, the pigment will combine with hydrogen ions or hydroxide ions and convert into the corresponding acid. Formula or basic type, thus showing different colors, because the pH indicator can produce reversible color changes in solutions of different pH values, so in the neutralization analysis, it can indicate the end of the reaction, and can measure the pH value of the test solution. Commonly used pH indicators in the laboratory include: phenol red, Congo red, methyl orange, phenolphthalein, thymol blue, litmus, methyl violet, malachite green, methyl yellow, bromophenol blue, bromocresol green, Methyl red, bromocresol violet, bromothymol blue, thymolphthalein (Thymolphthalein), alizarin yellow R, etc.

The preferred redox indicator of the ion layer of the present invention is methylene blue (Methylene blue, C ₁₆ H ₁₈ ClN ₃ S 3H ₂ O), dichlorophenol indophenol sodium (Dichlorophenolindophenol sodium, C ₁₂ H ₆ Cl ₂ NNaO ₂ ), N-phenylanthranilic acid (C ₁₃ H ₁₁ NO ₂ ), sodium diphenylamine sulfonate (C ₁₂ H ₁₀ NNaO ₃ S), N, N′-diphenylbenzidine (N, N’- Diphenylbenzidine, C ₂₀ H ₂₀ N ₂ ) or Methyl Viologen. The preferred pH indicator is Variamine Blue B Diazonium salt (C ₁₃ H ₁₂ ClN ₃ O).

The inorganic material of the ion layer 24 is an inorganic derivative.

The inorganic derivative is a halogen group (VIIA), oxygen group (VIA), nitrogen group (VA), carbon group (IVA), boron group (IIIA), alkaline earth group (IIA) or alkali metal group (IA); or Oxides, sulfides, chlorides or hydroxides of transition elements.

The transition elements are scandium subgroup (IIIB), titanium subgroup (IVB), vanadium subgroup (VB), chromium subgroup (VIB), manganese subgroup (VIIB), iron series (VIII), copper subgroup (IB ), zinc subgroup (IIB) or platinum group (VIII).

Here are examples of the above-mentioned groups:

Halogen (English VIIA):

Solid: I ₂ purple black; ICl dark red; IBr dark gray; IF ₃ yellow; ICl ₃ orange; I ₂ O ₅ white; I ₂ O ₄ yellow (ionic crystal); I ₄ O ₉ yellow (ionic crystal).

Oxygen group (English VIA):

Solid: S light yellow; Se gray, brown; Te colorless metallic luster; Na ₂ S, (NH ₄ ) ₂ S, K ₂ S, BaS white, soluble; ZnS white ↓; MnS meat red ↓; FeS black ↓ ; PbS black ↓; CdS yellow ↓; Sb ₂ S ₃ orange red ↓; SnS brown ↓; HgS black (precipitation), red (cinnabar); Ag ₂ S black ↓; CuS black ↓; Na ₂ S ₂ O ₃ white; Na ₂ S ₂ O ₄ white; SeO ₂ white, volatile; SeBr ₂ red; SeBr ₄ yellow; TeO ₂ white heated to yellow; H ₂ TeO ₃ white; TeBr ₂ brown; TeBr ₄ orange; TeI ₄ gray black; PoO ₂ Low-temperature yellow (face-centered cubic), high-temperature red (square); SO ₃ is colorless; SeO ₃ is colorless and deliquescent; TeO ₃ is orange; H ₆ TeO ₆ is colorless.

Nitrogen (English VA):

Solid: ammonium salt colorless crystal; metal nitride white; N ₂ O ₃ blue (low temperature); N ₂ O ₅ white; P white, red, black; P ₂ O ₃ white; P ₂ O ₅ white; PBr ₃ Yellow; PI ₃ red; PCl ₅ colorless; P ₄ Sx yellow; P ₂ S ₃ gray yellow; P ₂ S ₅ light yellow; H ₄ P ₂ O ₇ colorless glass; H ₃ PO ₂ white; As gray; As ₂ O ₃ white; As ₂ O ₅ white; AsI ₃ red; As ₄ S ₄ red (realgar); As ₄ S ₆ yellow (orpiment); As ₂ S ₅ light yellow; Sb silver white; Sb(OH) ₃ white ↓; Sb ₂ O ₃ white (antimony white, pigment); Sb ₂ O ₅ light yellow; SbX ₃ (X<>I) white; SbI ₃ red; Sb ₂ S ₃ orange ↓; Sb ₂ S ₅ orange; Bi silver white Slightly red; Bi ₂ O ₃ pale yellow; Bi ₂ O ₅ reddish brown; BiF ₃ off-white; BiCl ₃ white; BiBr ₃ yellow; BiI ₃ black ↓; Bi ₂ S ₃ brown-black.

Carbon group (English IVA):

Solid: C (diamond) colorless and transparent; C (graphite) black metallic luster; Si gray-black metallic luster; Ge gray-white; Sn silver-white; Pb dark gray; SiO ₂ colorless and transparent; H ₂ SiO ₃ colorless and transparent gel↓ ; Na ₂ SiF ₆ white crystal; GeO black; GeO ₂ white; SnO black; SnO ₂ white; Sn(OH) ₂ white ↓; PbO yellow or yellow red; Pb ₂ O ₃ orange; Pb ₃ O ₄ red; PbO ₂ Brown; CBr ₄ light yellow; CI ₄ light red; GeI ₂ orange; GeBr ₂ yellow; GeF ₄ white; GeBr ₄ off-white _; GeI ₄ yellow; SnF 2 white; SnCl ₂ white; SnBr ₂ light yellow; SnI ₂ orange; SnF ₄ white; SnBr ₄ colorless; SnI ₄ red; PbF ₂ colorless ↓; PbCl ₂ white ↓; PbBr ₂ white; PbI ₂ golden; PbF ₄ colorless; GeS red; GeS ₂ white; SnS brown ↓; SnS ₂ golden (commonly known as "gold powder") ↓; PbS black ↓; PbS ₂ reddish brown; Pb(NO ₃ ) ₂ colorless; Pb(Ac) ₂ 3H ₂ O colorless crystal; PbSO ₄ white ↓; PbCO ₃ white ↓; Pb( OH) ₂ white ↓; Pb ₃ (CO ₃ ) ₂ (OH) ₂ lead white ↓; PbCrO ₄ bright yellow ↓.

Boron group (English IIIA):

Solid: B (amorphous) brown powder; B (crystal) black gray; Al silver white; Ga silver white (easy to liquefy); In silver gray; Tl silver gray; B ₂ O ₃ glassy; H ₃ BO ₃ colorless flakes; BN White; Na ₂ B ₄ O ₇ 10H ₂ O white crystal; Cu(BO ₂ ) ₂ blue ↓; Ni(BO ₂ ) ₂ green ↓; NaBO ₂ Co(BO ₂ ) ₂ blue ↓; NaBO ₂ 4H ₂ O colorless Crystal; anhydrous NaBO ₂ yellow crystal; Al ₂ O ₃ white crystal; AlF ₃ colorless; AlCl ₃ white; AlBr ₃ white; AlI ₃ brown; Al(OH) ₃ white ↓; Ga ₂ O ₃ white ↓Ga(OH ) ₃ white ↓; GaBr ₃ white; GaI ₃ yellow; In ₂ O ₃ yellow; InBr ₃ white; InI ₃ yellow; TlOH yellow; Tl ₂ O black; Tl ₂ O ₃ brown black; TlCl white ↓; TlI yellow ↓ (similar to silver); TlBr ₃ yellow; TlI ₃ black.

Alkaline earth (English IIA):

Simple substance: silver white

Flame color: Ca brick red; Sr magenta; Ba green.

Oxides: all white solids.

Hydroxide: white solid Be(OH) ₂ ↓, Mg(OH) ₂ ↓.

Salt: mostly colorless or white crystals; BeCl ₂ light yellow; BaCrO ₄ yellow ↓; CaF ₂ white ↓.

Alkali metal (English IA):

Simple substance: silver white

Flame color: Li red; Na yellow; K purple; Rb purple; Cs purple.

Oxides, peroxides, superoxides, ozonides: Li ₂ O white; Na ₂ O white; K ₂ O light yellow; Rb ₂ O bright yellow; Cs ₂ O orange red; Na ₂ O ₂ light yellow; KO ₂ Orange yellow; RbO ₂ dark brown; CsO ₂ dark yellow; KO ₃ orange.

Hydroxide: white, LiOH white ↓.

Salt: mostly colorless or white crystals and easily soluble in water.

Insoluble salt ↓ (those not specified are all white crystals): LiF Li ₂ CO ₃ Li ₃ PO ₄ LiKFeIO ₆ Na【Sb(OH) ₆ 】NaZn(UO ₂ ) ₃ (Ac) ₉ 6H ₂ O yellow-green; M =K, Rb, Cs M ₃ [Co(NO ₂ ) ₆ ] bright yellow; MBPh ₄ MClO ₄ M ₂ PtCl ₆ light yellow; CsAuCl ₄ .

Copper subgroup (English IB):

Elemental substance: Cu purple red or dark red; Ag silver white; Au golden yellow.

Copper compounds: flame green; CuF red; CuCl white ↓; CuBr yellow ↓; CuI brown yellow ↓; CuCN white ↓; Cu ₂ O dark red; Cu ₂ S black; CuF ₂ white; CuCl ₂ brown yellow (solution yellow green ); CuBr ₂ brown; Cu(CN) ₂ brown yellow; CuO black ↓; CuS black ↓; CuSO ₄ colorless; CuSO ₄ 5H ₂ O blue; Cu(OH) ₂ light blue ↓; Cu(OH) ₂ CuCO ₃ Dark green; 【Cu(H ₂ O) ₄ 】 ²⁺ blue; 【Cu(OH) ₄ 】 ^2- blue-purple; 【Cu(NH ₃ ) ₄ 】 ²⁺ dark blue; 【CuCl ₄ 】 ^2- yellow; 【Cu( en) ₂ 】 ²⁺ deep blue-violet; Cu ₂ 【Fe(CN) ₆ 】brown red; alkyne copper red ↓.

Silver compounds: AgOH white (decomposed at room temperature); Ag ₂ O black; new AgOH brown yellow (mixed with Ag ₂ O); protein silver (AgNO ₃ drops on hand) black ↓; AgF white; AgCl white ↓; AgBr light yellow ↓ ; AgI yellow ↓ (colloid); Ag ₂ S black ↓; Ag ₄ [Fe(CN) ₆ ] white ↓; Ag ₃ [Fe(CN) ₆ ] white ↓; Ag ⁺ , [Ag(NH ₃ ) ₂ ] ⁺ , 【Ag(S ₂ O ₃ ) ₂ 】 ^3- , 【Ag(CN) ₂ 】 ^-colorless .

Gold compounds: HAuCl ₄ 3H ₂ O bright yellow crystals; KAuCl ₄ 1.5H ₂ O colorless flaky crystals; Au ₂ O ₃ black; H【Au(NO ₃ ) ₄ 】.3H ₂ O yellow crystals; AuBr grayish yellow↓ ; AuI lemon yellow ↓.

Zinc subgroup (I, IB):

Elemental substance: all are silvery white, and the precipitation of Hg in aqueous solution is black.

Zinc compound: ZnO white (zinc white pigment) ↓; ZnI ₂ colorless; ZnS white ↓; ZnCl ₂ white crystal (high solubility, acidic aqueous solution); K ₃ Zn ₃ 【Fe(CN) ₆ 】white; Zn ₃ 【 Fe(CN) ₆ 】 ₂ yellowish brown.

Cadmium compounds: CdO brown gray ↓; CdI ₂ yellow; CdS yellow (cadmium yellow pigment) ↓; HgCl ₂ (mercuric liter) white; HgNH ₂ Cl white ↓; Hg ₂ Cl ₂ (calomel) white ↓.

Mercury compounds: HgO red (large grain) or yellow (small grain) ↓; HgI ₂ red or yellow (slightly soluble); HgS black or red ↓; Hg ₂ NI H ₂ O red ↓; Hg ₂ (NO ₃ ) ₂ colorless crystals.

ZnS phosphor: Ag blue; Cu yellow-green; Mn orange.

Titanium subgroup (English IVB):

Titanium compound: Ti ³⁺ purple; [TiO(H ₂ O ₂ ) ₂ ] ²⁺ orange; H ₂ TiO ₃ white ↓; TiO ₂ white (titanium white pigment) or pink (rutile) ↓; (NH ₄ ) ₂ TiCl ₆ yellow crystals; [Ti(H ₂ O) ₆ ] Cl ₃ purple crystals; [Ti(H ₂ O) ₅ Cl] Cl ₂ H ₂ O green crystals; TiCl ₄ colorless fuming liquid.

Zirconium, hafnium: MO ₂ , MCl ₄ white.

Vanadium subgroup (English VB):

Vanadium compounds: V ²⁺ purple; V ³⁺ green; VO ²⁺ blue; V(OH) ^4- yellow; VO ₄ ^3- yellow; VO black; V ₂ O ₃ gray-black; V ₂ S ₃ brown-black; VO ₂ blue solid; VF ₄ green solid; VCl _{4 dark brown liquid; VBr 4 magenta} liquid; V ₂ O ₅ yellow or brick red; hydrated V 2 O ₅ brownish red; saturated _{V 2 O 5} solution (slightly soluble) pale Yellow; [VO ₂ (O ₂ ) ₂ ] ^3- yellow; [V(O ₂ ) ₃ ] ^3- red brown.

Condensation of vanadate: light yellow-dark red-light yellow as the ratio of the number of vanadium oxygen atoms decreases.

Niobium, tantalum: slightly.

Chromium subgroup (English VIB):

Chromium compounds: Cr ²⁺ blue; Cr ³⁺ purple; Cr2O7 ^2- orange red; CrO4 ^2- yellow; Cr(OH) ^4- bright green; Cr(OH) ₃ gray blue; Cr ₂ O ₃ green; CrO ₃ dark red Acicular; [CrO(O ₂ ) ₂ ] OEt ₂ blue; CrO ₂ Cl ₂ dark red liquid; Na ₂ Cr ₂ O ₇ , K ₂ CrO ₇ orange red; Ag ₂ CrO ₄ brick red ↓; BaCrO ₄ yellow ↓; PbCrO ₄ yellow ↓.

Purple Cr ₂ (SO ₄ ) ₃ 18H ₂ O——>Green Cr ₂ (SO ₄ ) ₃ 6H ₂ O——>Pink Cr ₂ (SO ₄ ) ₃

Dark green [Cr(H ₂ O) ₄ Cl ₂ ]Cl-cooled HCl->purple [Cr(H ₂ O) ₆ ]Cl ₃ -ether HCl->light green [Cr(H ₂ O) ₅ Cl]Cl ₂

【Cr(H ₂ O) ₆ 】 ³⁺ purple;【Cr(H ₂ O) ₄ (NH ₃ ) ₂ 】 ³⁺ purple red;【Cr(H ₂ O) ₃ (NH ₃ ) ₃ 】 ³⁺ light red; 【Cr(H ₂ O) ₂ (NH ₃ ) ₄ 】 ³⁺ orange red; 【Cr(NH ₃ ) ₅ H ₂ O】 ³⁺ orange yellow; 【Cr(NH ₃ ) ₆ 】 ³⁺ yellow.

Molybdenum, tungsten: MoO ₃ white; brown MoCl ₃ ; green MoCl ₅ ; MoS ₃ brown ↓; (NH ₄ ) ₃ [P(Mol ₂ O ₄ O)].6H ₂ O yellow crystal ↓; WO ₃ deep yellow; H ₂ WO ₄ xH ₂ O white colloid.

Manganese subgroup (English VIIB):

Manganese compounds: Mn ²⁺ meat red; Mn ³⁺ purple; MnO ₄ ^2- green; MnO ^4- purple; MnO ³⁺ bright green; Mn(OH) ₂ white ↓; MnO(OH) ₂ brown ↓; MnO ₂ black ↓; Anhydrous manganese salt (MnSO ₄ ) white crystal; Hexahydrate manganese salt (MnX ₂ 6H ₂ O, X=halogen, NO ₃ , ClO ₄ ) pink; MnS nH ₂ O meat red ↓; Anhydrous MnS dark green; MnCO ₃ white ↓; Mn ₃ (PO ₄ ) ₂ white ↓; KMnO ₄ purple red; K ₂ MnO ₄ green; K ₂ [MnF ₆ ] golden yellow crystal; Mn ₂ O ₇ brown oily liquid.

Technetium, rhenium: omitted.

Iron series (group VIII of the fourth cycle):

Iron compounds: Fe ²⁺ light green; [Fe(H ₂ O) ₆ ] ³⁺ light purple; [Fe(OH)(H ₂ O) ₅ ] ²⁺ yellow; FeO ₄ ^2- purple red; FeO black; Fe ₂ O ₃ dark red; Fe(OH)2 white ↓; Fe(OH) ₃ brown red ↓; FeCl ₃ or FeCl ₂ crystal brown red blue; anhydrous FeSO ₄ white; FeSO ₄ 7H ₂ O green; K ₄ [Fe( CN) ₆ 】(yellow blood salt) yellow crystal; K ₃ 【Fe(CN) ₆ 】(red blood salt) red crystal; Fe ₂ 【Fe(CN) ₆ 】Prussian blue↓; Fe【Fe(CN) ₆ 】 Black ↓; Fe(C ₅ H ₅ ) ₂ (ferrocene) orange-yellow crystal; M ₂ Fe ₆ (SO ₄ ) ₄ (OH) ₁₂ (jarosite, M=NH ₄ , Na, K) light yellow crystal ; Fe(CO) ₅ yellow liquid.

Cobalt compounds: Co ²⁺ pink; CoO gray green; Co ₃ O ₄ black; Co(OH) ₃ brown ↓; Co(OH) ₂ pink ↓; Co(CN) ₂ red; K ₄ [Co(CN) ₆ ] Purple crystals; Co ₂ (CO) ₈ yellow crystals; [Co(SCN) ₆ ] ^4- purple;

Cobalt chloride dehydration discoloration: pink CoCl ₂ 6H ₂ O-325K->purple red CoCl ₂ 2H ₂ O-313K->blue violet CoCl ₂ H ₂ O-393K->blue CoCl ₂ .

Nickel compounds: Ni ²⁺ bright green; 【Ni(NH ₃ ) ₆ 】 ²⁺ purple; Ni(OH) ₂ green ↓; Ni(OH) ₃ black ↓; anhydrous Ni(II) salt yellow; Na ₂ 【Ni (CN) ₄ ] yellow; K ₂ [Ni(CN) ₄ ] orange; Ni(CO) ₄ colorless liquid.

Platinum group elements (group VIII of the fifth and sixth periods):

Os blue-gray volatile solid; Pd↓(aq) black; OsO ₄ colorless gas with special odor; H ₂ PtCl ₆ orange-red crystals; Na ₂ PtCl ₆ orange-yellow crystals; M ₂ PtCl ₆ (M=K, Rb, Cs, NH ₄ ) yellow ↓.

The preferable inorganic material of the ion layer 24 is ferrous chloride (FeCl ₂ ), ferric chloride (FeCl ₃ ), titanium trichloride (TiCl ₃ ) or titanium tetrachloride (TiCl ₄ ).

In addition, the ion layer 24 may further contain at least one inert conductive salt, which may be lithium, sodium or tetraalkylamine salt. Suitable anions for the above-mentioned conductive salts, especially as inert and colorless anions for redox in metal salts can be: tetrafluoroborate ion, tetraphenylborate ion, cyanotriphenylborate ion, tetramethoxyborate ion Ion, perchlorate ion, chloride ion, nitrate ion, sulfate ion, phosphate ion, methanesulfonate ion, ethanesulfonate ion, tetradecanesulfonate ion, pentadecanesulfonate ion, trifluoromethane Sulfonate ion, perfluorobutanesulfonate ion, perfluorooctanesulfonate ion, benzenesulfonate ion, chlorobenzenesulfonate ion, toluenesulfonate ion, butylbenzenesulfonate ion, tertiary butylsulfonate ion , dodecylbenzenesulfonate ion, trifluoromethylbenzenesulfonate ion, hexafluorophosphate ion, hexafluoroarsenate ion, hexafluorosilicate ion, etc.

The solvent system of the ion layer 24 is dimethyl sulfoxide [(CH ₃ ) ₂ SO], propylene carbonate (C ₄ H ₆ O ₃ ), water (H ₂ O), γ-butyrolactone, acetonitrile, propane Nitrile, benzonitrile, glutaronitrile, methylglutaronitrile, 3,3'-oxodipropionitrile, hydroxypropionitrile, dimethylformamide, N-methylpyrrolidone, sulfolane, 3-methylsulfolane or a mixture thereof.

When the ion layer 24 is used as an auxiliary discoloration layer or another discoloration layer, its discoloration mechanism is, for example, dissolving ferric chloride (FeCl ₂ ) and methylene blue in dimethyl ethyl sulfone (DMSO) to form a complementary system of electrons. Chromogenic solution, the color of ferric chloride crystal particles is blue (Fe ²⁺ is blue), the surface oxidation will form reddish brown (Fe ³⁺ is light yellow), ferric chloride is dissolved in the solvent, that is, due to oxidation From Fe ²⁺ to Fe ³⁺ , the solvent becomes light yellow, and electrons are provided by the first transparent conductive element 211. When the methylene blue molecules close to the first transparent conductive element 211 obtain electrons, a reduction reaction occurs, Make methylene blue into a free radical, and when the external voltage is removed, the electric potential energy of Fe ³⁺ and methylene blue free radical is different, and electrons will spontaneously transfer from methylene blue free radical to Fe ³⁺ , then light yellow Fe ³⁺ is reduced to blue Fe ²⁺ , and then the entire ion layer 24 changes from light yellow to blue due to the valence change due to the reduction, achieving the effect of darkening the color, and it can be adjusted by adjusting the electrochromic solution. The color display effect of the ion layer 24 is controlled by the concentration, the potential difference, the polarity of the solvent, the pH value, the distance between the two electrodes and the difference in the dielectric constant.

In order to achieve a better effect, the best color of the electrochromic barrier is black, dark gray, dark brown or dark brown, and has a light transmittance of less than 20%, but in order to achieve such a dark shape, the voltage It is often required to be higher, so it is easy to reduce the life of the electrochromic layer 23. Therefore, the electrochromic layer 23 and the ion layer 24 are complementary to the color change method, and the concept of mixing different colors RGB to achieve a low driving voltage can produce deep color effect.

In order to achieve the above-mentioned black, black gray, dark brown or dark brown and other dark-color shading effects, the present invention can stack multiple electrochromic layers to achieve it by means of complementary colors. Please refer to FIG. The third embodiment is a schematic diagram of an electrochromic module with two layers of electrochromic layers stacked on top of each other. Another electrochromic layer 231 is further provided on the surface of the electrochromic layer 23. For example, the ion layer 24 is made of phenothiazine ( phenothiazine), its coloring state is green, and the electrochromic layer 23 is cobalt oxide (CoOx), its coloring state is red, and the electrochromic layer 231 is Prussian blue Fe ₄ [Fe( CN) ₆ ] ₃ , its coloring state is blue or brown, and the shading effect is achieved through the three-color mixing of green, red and blue; or the electrochromic layer 23 and the electrochromic layer 231 can be selected from Prussian blue Fe ₄ [Fe(CN) ₆ ] ₃ and vanadium pentoxide (V ₂ O ₅ ), the coloring state of vanadium pentoxide is gray, and the shading effect is achieved by mixing dark blue and gray colors; or selected from Fe ₄ [Fe (CN) ₆ ] ₃ and Fe ₄ [Ru(CN) ₆ ] ₃ , the colored state of Fe ₄ [Ru(CN) ₆ ] ₃ is purple, and the shading effect is achieved by mixing blue and purple colors.

Please refer to FIG. 25 , which is a schematic diagram of an electrochromic module with three layers of electrochromic layers stacked according to the fourteenth embodiment of the present invention, and another electrochromic layer is further provided on the surface of the electrochromic layer 231 in the thirteenth embodiment. The electrochromic layer 232 utilizes the color change of the multi-layer electrochromic material to cause color mixing, so as to achieve a better shading effect of dark colors.

Please refer to Fig. 26 and Fig. 27, which are designs according to the thirteenth and fourteenth embodiments of the present invention combined with the sixth embodiment of the present invention, but the drawings are only for illustration, the multi-layer electrochromic layer The design of the structure can be implemented in combination with any aspect of the above-mentioned various electrochromic modules.

Next, please refer to FIG. 28 , which is a schematic diagram of a stereoscopic imaging display device in which a plurality of electrochromic modules are arranged in one image display module according to a fifteenth embodiment of the present invention. As shown in the figure, the stereoscopic imaging display device includes an image display module 3 for displaying a planar image and a stereoscopic image; and a plurality of electrochromic modules 2 arranged on the surface of the image display module 3 . The structures of the electrochromic modules 2 are the same as those of the above-mentioned embodiments of the electrochromic modules, so they will not be repeated here. When it is desired to display a three-dimensional image, negative voltage is applied to the electrochromic modules 2 to make them colored and used as gratings, so that the left and right eyes receive different images to generate parallax, and finally fuse into a three-dimensional image in the brain. And if it is desired to display a flat image, it is only necessary to apply a positive voltage to the electrochromic modules 2 to fade the color and make the grating disappear.

Alternatively, the method shown in FIG. 29 can be used. FIG. 29 is a schematic diagram of a stereoscopic imaging display device in which the electrochromic module of FIG. 16 is provided in an image display module according to a sixteenth embodiment of the present invention. The stereoscopic imaging display device includes an image display module 3 for displaying a plane image and a stereoscopic image; and an electrochromic module 2 arranged on the surface of the image display module 3, wherein the electrochromic module 2 has multiple An electrochromic layer 23. The structure of the electrochromic module 2 is the same as that of the above embodiments of the electrochromic modules with multiple electrochromic layers 23 , so it will not be repeated here. When it is desired to display a three-dimensional image, by applying a negative voltage to the electrochromic modules 2, the electrochromic layers 23 are colored to be used as gratings, so that the left and right eyes receive different images to generate parallax, and finally the brain merged into a stereoscopic image. However, if a planar image is to be displayed, it is only necessary to apply a positive voltage to the electrochromic modules 2 to fade the electrochromic layers 23 and make the gratings disappear.

However, the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; any equivalent or easy changes made by those who are familiar with this technology will not depart from the spirit and scope of the present invention. The equivalent changes and modifications made below shall all be covered within the patent scope of the present invention.

To sum up, the electrochromic module of the present invention and the stereoscopic imaging display device with the module conform to the novelty, advancement and industrial applicability stipulated in the patent law; Application for patent of invention.

Claims (80)

1. electrochromism module is characterized in that it includes:

One first substrate, its upper surface are provided with at least one first conducting element;

One second substrate;

At least one electrochromic layer is located between this first substrate and this second substrate; And

At least one sheath is located at this electrochromism laminar surface, and its material is that mixing one organic material and an inorganic material are dissolved in the solvent made.

2. electrochromism module as claimed in claim 1; It is characterized in that; When this first conducting element, this electrochromic layer and this sheath when being a plurality of, each this first conducting element is arranged to a storage tank form respectively, with ccontaining this electrochromic layer and this sheath.

3. electrochromism module as claimed in claim 1; It is characterized in that; When this first conducting element, this electrochromic layer and this sheath when being a plurality of, have more a plurality of blocker unit, be arranged between these a plurality of first conducting elements, these many electrochromic layers and this polyion layer.

4. electrochromism module as claimed in claim 3 is characterized in that, the material of these many blocker unit is a photoresistance.

5. electrochromism module as claimed in claim 1; It is characterized in that; When this first conducting element and this electrochromic layer when being a plurality of; How first conducting elements are staggered provides positive and negative voltage, and these many electrochromic layers are arranged to a storage tank form respectively, with ccontaining electronegative many first conducting elements that are somebody's turn to do.

6. electrochromism module as claimed in claim 1; It is characterized in that; When this first conducting element and this electrochromic layer when being a plurality of, these many first conducting elements are staggered provide positive and negative voltage, these many electrochromic layers be arranged at respectively electronegative should many first conducting elements on.

7. electrochromism module as claimed in claim 1 is characterized in that, has more at least one second conducting element, and this second conducting element is to should first conducting element and be located on the lower surface of this second substrate.

8. electrochromism module as claimed in claim 7; It is characterized in that; When this first conducting element, this second conducting element, this electrochromic layer and this sheath when being a plurality of; Each this first conducting element and this second conducting element are arranged to a storage tank form respectively, with ccontaining this electrochromic layer and this sheath.

9. electrochromism module as claimed in claim 7; It is characterized in that; When this first conducting element, this second conducting element, this electrochromic layer and this sheath when being a plurality of; Have more a plurality of blocker unit, be arranged between these many first conducting elements, these many second conducting elements, these many electrochromic layers and this polyion layer.

10. electrochromism module as claimed in claim 9 is characterized in that, the material of these many blocker unit is a photoresistance.

11. electrochromism module as claimed in claim 7; It is characterized in that; When this first conducting element and this electrochromic layer when being a plurality of, these many first conducting elements are staggered to provide positive and negative voltage, and this second conducting element provides positive voltage; These many electrochromic layers are arranged to a storage tank form respectively, with ccontaining electronegative many first conducting elements that are somebody's turn to do.

12. electrochromism module as claimed in claim 7; It is characterized in that; When this first conducting element and this electrochromic layer when being a plurality of; How first conducting elements are staggered provides positive and negative voltage, and this second conducting element provides positive voltage, and these many electrochromic layers are arranged at electronegative being somebody's turn to do on many first conducting elements respectively.

13. like the described electrochromism module of arbitrary claim in the claim 1 to 12; It is characterized in that, the material of this first substrate and this second substrate be plastic cement, high molecular weight plastic, glass or for be selected from plastic polymer group that resin, polyethylene terephthalate, polycarbonate, tygon, PVC, polypropylene and polystyrene and polymethylmethacrylate form one of them.

14. like the described electrochromism module of arbitrary claim in the claim 1 to 12; It is characterized in that, the material of this first conducting element be selected from that tin indium oxide, indium zinc oxide, zinc oxide aluminum and tin-antiomony oxide form mix one of them of oxide group.

15., it is characterized in that the material of this first conducting element is CNT or gathers-3,4-vinyl dioxy thiophene PEDOT conducting polymer material like the described electrochromism module of arbitrary claim in the claim 1 to 12.

16. like the described electrochromism module of arbitrary claim in the claim 1 to 12; It is characterized in that this electrochromic layer is the compound material of an organic electrochromic material, inorganic electrochromic material, transition metal oxide, transistion metal compound or transistion metal compound and organic electrochromic material.

17. electrochromism module as claimed in claim 16 is characterized in that, this organic electrochromic material is dipyridine, purple sieve essence, anthraquinone, four thiophene fulvalenes or pyrazoline oxidation-reduction type compound and derivant thereof.

18. electrochromism module as claimed in claim 16; It is characterized in that this organic electrochromic material is polyacetylene, polyaniline, polypyrrole, polythiophene, gather the 3-alkylthrophene, gather furans, polyphenylene sulfide, aromatic polyamide/polyimide or polyphenylacetylene conducting polymer and derivant thereof.

19. electrochromism module as claimed in claim 16 is characterized in that, this organic electrochromic material is for gathering metal complex and derivant thereof.

20. electrochromism module as claimed in claim 16 is characterized in that, coordination unit's complex compound and derivant thereof that this organic electrochromic material is transition metal and lanthanide series.

21. electrochromism module as claimed in claim 16 is characterized in that, this organic electrochromic material is metal phthalein cyanine and derivant thereof.

22. electrochromism module as claimed in claim 16 is characterized in that, the water-soluble solution of rhodanide that this organic electrochromic material is ferrocene, iron, six cyanic acid ferrites are dissolved in the four cyano quinone or four rhodanides are dissolved in acetonitrile.

23. electrochromism module as claimed in claim 16; It is characterized in that this transition metal oxide is to be selected from one of them of anode variable color transition metal oxide group that chromium oxide, nickel oxide, yttrium oxide, manganese oxide, nickel hydroxide and tantalum pentoxide form.

24. electrochromism module as claimed in claim 16 is characterized in that, this transition metal oxide is to be selected from one of them of negative electrode variable color transition metal oxide that tungsten oxide, molybdena, niobium oxide, titanium dioxide, strontium titanates and tantalum pentoxide form.

25. electrochromism module as claimed in claim 16 is characterized in that, this transition metal oxide is to be selected from one of them of the moon/anode variable color transition metal oxide group that vanadium oxide, rhodium oxide and cobalt oxide form.

26. electrochromism module as claimed in claim 16 is characterized in that, this transistion metal compound is Prussian blue.

27. electrochromism module as claimed in claim 16 is characterized in that, this inorganic electrochromic material is the C60 film of Li doped, K, Mg, Cr, Cu, Ba.

28., it is characterized in that the organic material of this sheath is redox indicator or pH indicator like the described electrochromism module of arbitrary claim in the claim 1 to 12.

29. electrochromism module as claimed in claim 28 is characterized in that, this redox indicator is methylenum careuleum, dichlorophenol indophenol sodium, N-phenylanthranilic acid, diphenylamine sulfonic acid sodium salt), N, N '-diphenylbenzidine or purpurine.

30. electrochromism module as claimed in claim 28 is characterized in that, this pH indicator is the blue salt B in all Lamines.

31., it is characterized in that the inorganic material of this sheath is an inorganic derivative like the described electrochromism module of arbitrary claim in the claim 1 to 12.

32. electrochromism module as claimed in claim 31 is characterized in that, this inorganic derivative is oxide, sulfide, chloride or the oxyhydroxide of transitional element.

33. electrochromism module as claimed in claim 32; It is characterized in that this transitional element is scandium subgroup (IIIB), titanium subgroup (IVB), vanadium subgroup (VB), chromium subgroup (VIB), manganese subgroup (VIIB), iron system (VIII), copper subgroup (IB), zinc subgroup (IIB) or platinum group (VIII).

34. electrochromism module as claimed in claim 31 is characterized in that, this inorganic derivative is halogen family (VIIA), chalcogen (VIA), nitrogen family (VA), carbon family (IVA), boron family (IIIA), alkaline earth (IIA) or alkali metal group (IA).

35., it is characterized in that the inorganic material of this sheath is iron protochloride (FeCl2), ferric trichloride (FeCl3), titanium trichloride (TiCl3) or titanium tetrachloride (TiCl4) like the described electrochromism module of arbitrary claim in the claim 1 to 12.

36. like the described electrochromism module of arbitrary claim in the claim 1 to 12; It is characterized in that; The solvent of this sheath is dimethyl sulfoxide (DMSO), carbonic allyl ester, water, gamma-butyrolacton, acetonitrile, propionitrile, benzene nitrile, glutaronitrile, methyl cellosolve acetate glutaronitrile, 3,3 '-oxydipropionitrile, hydroxypropionitrile, dimethyl formamide, N-methylpyrrole pyridine ketone, sulfolane, 3-methyl sulfolane or its potpourri.

37., it is characterized in that this sheath further contains at least a inertia conducting salt like the described electrochromism module of arbitrary claim in the claim 1 to 12.

38. like the 37th described electrochromism module of claim, wherein, this inertia conducting salt is lithium, sodium or tetraalkyl amine salt.

39. like the described electrochromism module of arbitrary claim in the claim 7 to 12; It is characterized in that, the material of this first conducting element and this second conducting element be selected from that tin indium oxide, indium zinc oxide, zinc oxide aluminum and tin-antiomony oxide form mix one of them of oxide group.

40., it is characterized in that the material of this first conducting element and this second conducting element is CNT or gathers-3,4-vinyl dioxy thiophene PEDOT conducting polymer material like the described electrochromism module of arbitrary claim in the claim 7 to 12.

41. a three-dimensional imaging display device is characterized in that it includes:

One image display module is in order to show a flat image and a stereopsis; And

One electrochromism module is arranged at this image display module surface, includes:

One first substrate, its upper surface are provided with at least one first conducting element;

One second substrate;

A plurality of electrochromic layers are located between this first substrate and this second substrate; And

At least one sheath is located at this electrochromism laminar surface, and its material is that mixing one organic material and an inorganic material are dissolved in the solvent made.

42. three-dimensional imaging display device as claimed in claim 41 is characterized in that, when this first conducting element and this sheath were a plurality of, each this first conducting element was arranged to a storage tank form respectively, with ccontaining this electrochromic layer and this sheath.

43. three-dimensional imaging display device as claimed in claim 41 is characterized in that, when this first conducting element and this sheath when being a plurality of, has more a plurality of blocker unit, is arranged between these many first conducting elements, these many electrochromic layers and this polyion layer.

44. three-dimensional imaging display device as claimed in claim 43 is characterized in that, the material of these many blocker unit is a photoresistance.

45. three-dimensional imaging display device as claimed in claim 41; It is characterized in that when this first conducting element was a plurality of, these many first conducting elements interlock provided positive and negative voltage; These many electrochromic layers are arranged to a storage tank form respectively, with ccontaining electronegative many first conducting elements that are somebody's turn to do.

46. three-dimensional imaging display device as claimed in claim 41 is characterized in that, when this first conducting element was a plurality of, the staggered positive and negative voltage, these many electrochromic layers of providing of these many first conducting elements was arranged at electronegative being somebody's turn to do on many first conducting elements respectively.

47. three-dimensional imaging display device as claimed in claim 41 is characterized in that, has more at least one second conducting element, to should first conducting element and be located on the lower surface of this second substrate.

48. three-dimensional imaging display device as claimed in claim 47; It is characterized in that; When this first conducting element, this second conducting element and this sheath are a plurality of; Each this first conducting element and this second conducting element are arranged to a storage tank form respectively, with ccontaining this electrochromic layer and this sheath.

49. three-dimensional imaging display device as claimed in claim 47; It is characterized in that; When this first conducting element, this second conducting element and this sheath when being a plurality of; Have more a plurality of blocker unit, be arranged between these many first conducting elements, these many second conducting elements, these many electrochromic layers and this polyion layer.

50. three-dimensional imaging display device as claimed in claim 49 is characterized in that, the material of these many blocker unit is a photoresistance.

51. three-dimensional imaging display device as claimed in claim 47; It is characterized in that when this first conducting element was a plurality of, these many first conducting elements interlock provided positive and negative voltage; These many electrochromic layers are arranged to a storage tank form respectively, with ccontaining electronegative many first conducting elements that are somebody's turn to do.

52. three-dimensional imaging display device as claimed in claim 47 is characterized in that, when this first conducting element was a plurality of, the staggered positive and negative voltage, these many electrochromic layers of providing of these many first conducting elements was arranged at electronegative being somebody's turn to do on many first conducting elements respectively.

53. like the described three-dimensional imaging display device of the arbitrary claim in the claim 41 to 52; It is characterized in that, the material of this first substrate and this second substrate be plastic cement, high molecular weight plastic, glass or for be selected from plastic polymer group that resin, polyethylene terephthalate, polycarbonate, tygon, PVC, polypropylene and polystyrene and polymethylmethacrylate form one of them.

54. like the described three-dimensional imaging display device of the arbitrary claim in the claim 41 to 52; It is characterized in that, the material of this first conducting element be selected from that tin indium oxide, indium zinc oxide, zinc oxide aluminum and tin-antiomony oxide form mix one of them of oxide group.

55., it is characterized in that the material of this first conducting element is CNT or gathers-3,4-vinyl dioxy thiophene PEDOT conducting polymer material like the described three-dimensional imaging display device of the arbitrary claim in the claim 41 to 52.

56. like the described three-dimensional imaging display device of the arbitrary claim in the claim 41 to 52; It is characterized in that this electrochromic layer is the compound material of an organic electrochromic material, inorganic electrochromic material, transition metal oxide, transistion metal compound or organic electrochromic material and transistion metal compound.

57. three-dimensional imaging display device as claimed in claim 56 is characterized in that, this organic electrochromic material is dipyridine, purple sieve essence, anthraquinone, four thiophene fulvalenes or pyrazoline oxidation-reduction type compound and derivant thereof.

58. three-dimensional imaging display device as claimed in claim 56; It is characterized in that this organic electrochromic material is polyacetylene, polyaniline, polypyrrole, polythiophene, gather the 3-alkylthrophene, gather furans, polyphenylene sulfide, aromatic polyamide/polyimide or polyphenylacetylene conducting polymer and derivant thereof.

59. three-dimensional imaging display device as claimed in claim 56 is characterized in that, this organic electrochromic material is for gathering metal complex and derivant thereof.

60. three-dimensional imaging display device as claimed in claim 56 is characterized in that, coordination unit's complex compound and derivant thereof that this organic electrochromic material is transition metal and lanthanide series.

61. three-dimensional imaging display device as claimed in claim 56 is characterized in that, this organic electrochromic material is metal phthalein cyanine and derivant thereof.

62. three-dimensional imaging display device as claimed in claim 56 is characterized in that, the water-soluble solution of rhodanide that this organic electrochromic material is ferrocene, iron, six cyanic acid ferrites are dissolved in the four cyano quinone or four rhodanides are dissolved in acetonitrile.

63. three-dimensional imaging display device as claimed in claim 56; It is characterized in that this transition metal oxide is to be selected from one of them of anode variable color transition metal oxide group that chromium oxide, nickel oxide, yttrium oxide, manganese oxide, nickel hydroxide and tantalum pentoxide form.

64. three-dimensional imaging display device as claimed in claim 56; It is characterized in that this transition metal oxide is to be selected from one of them of negative electrode variable color transition metal oxide that tungsten oxide, molybdena, niobium oxide, titanium dioxide, strontium titanates and tantalum pentoxide form.

65. three-dimensional imaging display device as claimed in claim 56 is characterized in that, this transition metal oxide is to be selected from one of them of the moon/anode variable color transition metal oxide group that vanadium oxide, rhodium oxide and cobalt oxide form.

66. three-dimensional imaging display device as claimed in claim 56 is characterized in that, this transistion metal compound is Prussian blue (Fe4 [Fe (CN) 6] 3).

67. three-dimensional imaging display device as claimed in claim 56 is characterized in that, this inorganic electrochromic material is the C60 film of Li doped, K, Mg, Cr, Cu, Ba.

68., it is characterized in that the organic material of this sheath is redox indicator or pH indicator like the described three-dimensional imaging display device of the arbitrary claim in the claim 41 to 52.

69. like the described three-dimensional imaging display device of claim 68; It is characterized in that; This redox indicator be methylenum careuleum (, dichlorophenol indophenol sodium (, N-phenylanthranilic acid (C13H11NO2), diphenylamine sulfonic acid sodium salt, N, N '-diphenylbenzidine (or purpurine.

70., it is characterized in that this pH indicator is the blue salt B in all Lamines like the described three-dimensional imaging display device of claim 68.

71., it is characterized in that the inorganic material of this sheath is an inorganic derivative like the described three-dimensional imaging display device of the arbitrary claim in the claim 41 to 52.

72., it is characterized in that this inorganic derivative is oxide, sulfide, chloride or the oxyhydroxide of transitional element like the described three-dimensional imaging display device of claim 71.

73. like the described three-dimensional imaging display device of claim 72; It is characterized in that this transitional element is scandium subgroup (IIIB), titanium subgroup (IVB), vanadium subgroup (VB), chromium subgroup (VIB), manganese subgroup (VIIB), iron system (VIII), copper subgroup (IB), zinc subgroup (IIB) or platinum group (VIII).

74., it is characterized in that this inorganic derivative is halogen family (VIIA), chalcogen (VIA), nitrogen family (VA), carbon family (IVA), boron family (IIIA), alkaline earth (IIA) or alkali metal group (IA) like the described three-dimensional imaging display device of claim 71.

75., it is characterized in that the inorganic material of this sheath is iron protochloride, ferric trichloride, titanium trichloride or titanium tetrachloride like the described three-dimensional imaging display device of the arbitrary claim in the claim 41 to 52.

76., it is characterized in that this sheath further contains at least a inertia conducting salt like the described three-dimensional imaging display device of the arbitrary claim in the claim 41 to 52.

77., it is characterized in that this inertia conducting salt is lithium, sodium or tetraalkyl amine salt like the described three-dimensional imaging display device of claim 76.

78. like the 41st to 52 each described three-dimensional imaging display device of claim; Wherein, The solvent of this sheath is dimethyl sulfoxide (DMSO), carbonic allyl ester, water, gamma-butyrolacton, acetonitrile, propionitrile, benzene nitrile, glutaronitrile, methyl cellosolve acetate glutaronitrile, 3,3 '-oxydipropionitrile, hydroxypropionitrile, dimethyl formamide, N-methylpyrrole pyridine ketone, sulfolane, 3-methyl sulfolane or its potpourri.

79. like the described three-dimensional imaging display device of the arbitrary claim in the claim 47 to 52; It is characterized in that; (Antimony Tin Oxide, that ATO) is formed mixes one of them of oxide group to the material of this first conducting element and this second conducting element in order to be selected from tin indium oxide, indium zinc oxide, zinc oxide aluminum and tin-antiomony oxide.

80., it is characterized in that the material of this first conducting element and this second conducting element is CNT or gathers-3,4-vinyl dioxy thiophene conducting polymer material like the described three-dimensional imaging display device of the arbitrary claim in the claim 47 to 52.

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