WO2008049275A1

WO2008049275A1 - Flexible electromic apparatus

Info

Publication number: WO2008049275A1
Application number: PCT/CN2006/002857
Authority: WO
Inventors: Young-Sen Lin; Chih-Chieh Chan
Original assignee: Feng Chia University; Mobiletron Electronics Co., Ltd.
Priority date: 2006-10-25
Filing date: 2006-10-25
Publication date: 2008-05-02

Abstract

A flexible electrochromic apparatus includes: a first high molecular substrate, a second high molecular substrate and a middle layer which includes a first conduction layer, an electrochromic layer, an ion conduction layer, an aid electrochromic layer and a second conduction layer which are arranged in this order from the first high molecular substrate to the second high molecular substrate.The electrochromic layer is selected from the group consisting of tungsten oxide, molybdenum oxide, titanium oxide, columbium oxide, iridium oxide and the combination thereof. The aid electrochromic layer is selected from the group consisting of vanadium oxide, nickel oxide, chromic oxide, manganese oxide, iron oxide, copper oxide, rhodium oxide and the combination thereof.

Description

Flexible electrochromic device

Technical field

The present invention is directed to an electrochromic device, and more particularly to a flexible electrochromic device. Once

Back technology

Electrochromic materials can be used in various fields, such as: vehicle mosaic glass (such as window, skylight), building mosaic glass, display device, optical components, mirror body and electromagnetic wave shielding, etc. Effectively block the interference of the outside world (such as light, heat). Electrochromic materials are generally classified into organic materials and inorganic materials, and for stability, inorganic materials are preferred, such as tungsten oxide, titanium oxide, and the like.

It is known that electrochromic devices mostly use glass as a substrate, and in practical use, they are often limited to the material of the substrate and cannot be bent at will, and their use is limited. In addition, it is known that electrochromic devices cannot be fabricated using a tape-and-reel type (r 0 1 1 t 0 r o l 1 ), making it impossible to provide a low-cost electrochromic color.

U.S. Patent No. 6, 1 9 3 3 7 9 discloses that an electrochromic device is mainly used for rearview mirrors in a vehicle (rear V iewmirr 0 r ). See Figure 1 for the electrochromic device. a front element 1 0 0 having a "front surface 1 0 0 a and a -, · '. - ~ - rear surface 1 0 0 b , a spacing from the element 1 0 0 and having a front surface 1 0 1 a and a rear surface 1 0 1 b of the rear element 1 0 1 , a rear surface 1 0 0 b disposed on the front element 1 0 0

, .

Transparent conductive layer 1 0 2 , ― surface set on the rear component 1 0 1 1 0

a conductive layer 1 0 3 on 1 b and a sealing member 1 0 4 disposed between the transparent conductive layer 1 0 2 and the conductive layer 1 0 3. wherein the sealing member 10

4 The transparent conductive layer 1 0 2 and the conductive layer 1 0 3 are mutually coupled to form a compartment 1 0 5 , and the anode 10 5 is accommodated in a solution-like electrochromic color. The variable material, the electrochromic material may be composed of an inorganic metal oxide or an organic material. The electrochromic material of the electrochromic device of this patent is mixed with the electrolyte for conducting ions, so it is necessary to continuously pass a higher voltage to maintain the discoloration state, and thus cannot have color memory effect. ) The effect. In addition, since the electrochromic material is filled into the compartment in the form of a solution, the surface of the substrate of this patent must be a polymer which is completely exposed to an organic solvent and which retains its properties and contains an aliphatic hydrocarbon. Materials, but this patent does not mention or teach that the substrate is flexible, and the electrochromic material contained in the chamber is in the form of a solution, which may cause the electrochromic color when the entire device is bent. The material is exposed, which also affects the scope of subsequent applications.

Ba ye r Company has obtained a series of UV stabilized electrochromic components

( UV s t a b i 1 i z e d el e c t r 0 C h r 0 m i c assembly )

3⁄4 Patent No. 6 1 5 7 4 7 9 6 3 2 3 , 9 8 8

6 3 2 7 0 7 0 and 6 4 5 2 7 1 1). For example, U.S. Patent No. 6,1,7,7,7,9, discloses an electrochromic component comprising a substrate 20 0 a conductive coating 2 0 1 and an electrochromic layer 2 0 from top to bottom. 2 - electrolyte layer 2 0 3 , an ion storage layer 2 0 4

― Conductive coating 2 0 5 and a substrate 2 0 6 (see Figure 2). The two substrates 2

0 0 2 0 6 can be made of glass or any plastic, the two conductive coatings 2

0 1 2 0 5 can be made of metal oxide (such as indium tin oxide) or metal (such as silver); electrochromic 5 layer 2 0 2 is composed of polydioxythiophene

( p 01 y d i 0 X y t h i 0 p h e n e ) The electrolyte layer 2 0 3 contains a polymer-lithium salt-solvent and a "lighting agent", and the ion storage layer 2

0 4 is made of group n of special metal oxides (eg Ti0 ₂ - Ce0 ₂ ). It is known that an organic polymer such as oxythiophene is highly susceptible to ultraviolet light and is liable to cause the electrochromic effect of the component to decay or even disappear. Therefore, in the patent, it is necessary to additionally add the light to the electrolyte layer 203. Stabilizer to avoid the influence of the ultraviolet light on the organic polymer. This patent does not mention or teach that the substrate is flexible and thus affects the scope of subsequent applications. From the above, it can be seen that for an electrochromic device having better stability, coloring memory, fast coloration, and adjustable coloration, there is still a need for considerable improvement in electrochromic devices. Summary of the invention

Therefore, the object of the present invention is to provide a flexible electrochromic device having better stability, coloring memory, fast color removal, and adjustable color depth.

Therefore, the flexible electrochromic device of the present invention comprises a flexible first polymer substrate, a flexible first polymer substrate disposed in parallel with the first polymer substrate, and a An intermediate unit between the first molecular substrate and the second polymer substrate - the intermediate unit sequentially includes: a first conductive layer from the first polymer substrate toward the second polymer substrate ,

An electrochromic layer, an ion conducting layer, an auxiliary electrochromic layer and a second conductive layer. Wherein the electrochromic layer is made of a metal oxide selected from the group consisting of tungsten oxide, molybdenum oxide, titanium oxide, cerium oxide, cerium oxide, and the like. The auxiliary electrochromic layer is selected from metal oxides in the group consisting of vanadium oxide, nickel oxide, chromium oxide, manganese oxide, iron oxide, copper oxide, cerium oxide, and the like. Group

Wait

The first and second substrates used in the present invention are all made of ruthenium molecules, so that the density and thickness of the ruthenium molecules can be controlled by the process, so that the first and second substrates have better flexibility and are utilized by them. It also has good light regulation after bending, which makes the subsequent use more extensive (such as automotive components (such as glass, sunroof, mirror), electronic paper, electronic products and smart windows, etc.

―Applications with curved surfaces). Moreover, since it is known that an organic polyPI material is used as an electrochromic material, it is easy to cause a problem that the electrochromic effect of the module is deteriorated or even disappeared after ultraviolet light irradiation, so the present invention The electrochromic device is formed by using an inorganic metal oxide which is not affected by ultraviolet rays to form an electrochromic layer, and is provided to assist in controlling the decoloring and coloring state. An auxiliary electrochromic layer, and an ion conducting layer for conducting ions to the electrochromic layer and the auxiliary electrochromic layer (such as the following two reversible reaction mechanisms) to effectively extend the coloring memory time

xLi' + WOa + xe"** LixWO (transparent blue)

Li _x V Li++ V ₂ 0 ₅ + xe— (very light blue yellow), by changing the magnitude of the voltage (or reverse voltage) and the voltage input time between the first and second conductive layers Adjusting the degree of coloration (or decoloration), so that the electrochromic device of the present invention has the advantages of better stability (especially anti-ultraviolet light property), coloring memory, fast decoloring, and adjustable coloration, especially When the flexible electrochromic device of the present invention is bent at 90°, it still has excellent light regulation. DRAWINGS

In order to further explain the specific technical content of the present invention, the following detailed description will be given in conjunction with the embodiments and the accompanying drawings, in which:

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an illustration of the structure of a known electrochromic device; Figure 2 is a schematic view of another known electrochromic device; Figure 3 is a schematic illustration of the practice of the present invention The structure of the light-transmissive electrochromic device of Example 1,

4 is a schematic view showing the case where the light transmissive flexible electrochromic device of Embodiment 1 of the present invention is bent by 90°;

Figure 5 is an ultraviolet light-visible light spectrum diagram illustrating an embodiment of the present invention

The result of the transmittance test of the light-transmissive flexible color-changing device of 1; FIG. 6 is a schematic view showing the structure of the light-reflecting flexible electrochromic device of Embodiment 4 of the present invention

Figure 7 is a schematic view showing the structure of a light-reflecting flexible electrochromic device of Embodiment 5 of the present invention

Figure 8 is an ultraviolet light-visible light spectrum diagram illustrating an embodiment of the present invention

5 is a result of a reflectance test performed by a light-reflecting flexible electrochromic device; FIG. 9 is a schematic view showing that the light reflection of Embodiment 6 of the present invention is flexible Structure of an electrochromic device,

Figure 10 is a diagram showing the structure of a light-reflecting flexible electrochromic device of Embodiment 7 of the present invention.

Figure 1 is a diagram showing the structure of a light-reflecting flexible electrochromic device of Embodiment 8 of the present invention, and

Figure 1 2 is a s diagram illustrating the structure of the light-reflective flexible color of the embodiment 9 of the present invention.

Change assembly

The flexible electrochromic device of the present invention comprises a flexible first polymer substrate, a flexible first polymer substrate disposed in parallel with the first polymer substrate, and a first molecular substrate disposed on the first molecular substrate And an intermediate unit between the second molecular substrate and the intermediate unit, the first conductive layer, the electrochromic layer, and the ion conductive layer are sequentially included in the direction of the first polymer substrate An auxiliary electrochromic layer, and - a second two conductive layer.

In the flexible electrochromic device of the present invention, the electrochromic layer is made of tungsten oxide, molybdenum oxide, titanium oxide, hafnium oxide and the like which are selected from the group consisting of the following oxides. A group of the auxiliary electrochromic layers are selected from metal oxides of the group consisting of vanadium oxide, nickel oxide, chromium oxide, manganese oxide, iron oxide, copper oxide, Cerium oxide and the like, and in a specific embodiment of the invention, the electrochromic layer is made of tungsten oxide, and the electrochromic layer is made of vanadium oxide.

The first molecular substrate and the first molecular substrate are required to have flexibility, that is, can be changed back to the original shape after folding, and are made of a polymer material.

Preferably, the first polymer substrate and the second polymer substrate are respectively made of a material selected from the group consisting of: polyethylene terephthalate: P 01 ye thyl ene terephthalate ), polyphthalate

(polycarbonate), acrylic (acrylic), and a combination of these.

The first conductive layer and the second conductive layer may be any gold having conductivity Made of genus, metal alloy or metal oxide. Preferably, the first conductive layer and the second conductive layer respectively comprise a metal oxide selected from the group consisting of tin oxide (tin _0X ide), indium tin oxide (iridium tin)

0 X id e) , antimony tin 0 i d e fluorine-doped tin oxide

( f 1 u 0 r i ■ne - doped tin oxide ), fluorinated 铱 tin ί ( i r i di u m tin

0 X i de ) , zinc oxide and a group of none or alternatively the first conductive layer contains a silver, aluminum and the like selected from the group consisting of a combination, and the second conductive layer comprises a metal oxide selected from the group consisting of: tin oxide, indium tin oxide, antimony tin oxide, fluorine-doped tin oxide, antimony tin fluoride, oxidation Zinc and the combination of these. Alternatively, the first conductive layer contains a metal oxide selected from the group consisting of tin oxide, indium tin oxide, antimony tin oxide doped tin oxide, antimony tin fluoride, The zinc oxide and the set of n and the second conductive layer comprise a combination of silver, aluminum and the like selected from the group consisting of the following. In a specific embodiment of the present invention, the first conductive layer and the second conductive layer are both made of indium tin oxide. In another specific example, the first conductive layer and the second conductive layer are each made of indium tin oxide. And silver constitute o

Preferably, the ion conducting layer is gel and contains a lithium-containing salt, a dispersing agent, and a thickening agent. It is known that solid electrolytes (for example, iNb0 ₃ or Ta ₂ 0 need to be colored or decolored after continuous application of a higher voltage, and it takes a long time, and a gel-like ion conductive layer can effectively increase ions. Conduction speed, and shorten the de-coloring/coloring time, and only need to apply a lower voltage to complete the decoloring or coloring state. It is also worth mentioning that when the flexible electrochromic device is bent, because The first substrate and the second substrate are both flexible, and the ion conductive layer is gel-like on the force port, and the stress is more effectively released, so that leakage of the liquid electrolyte does not occur.

Preferably, the lithium-containing salt is selected from the group consisting of lithium perchlorate [LiCO, J, lithium trifluoromethanesulfonamide [LiN (S0 ₂ CF a ), ·, "", lithium fluoromethanesulfonate [Li0 ₃ SCF ₃ ], lithium nonafluorobutane sulfonate [LiO 3 SC 4 F 9 ], chlorine Lithium [Li CI], lithium hexafluorophosphate [LiPF ₆ ], and a combination of these.

Preferably, the dispersing agent for the ion conducting layer is selected from the group consisting of propylene carbonate, ethylene carbonate, and Y-butyrolactone. ( y -butyrolactone ) s acetonitrile dimethyl methamine ( dimethyl f ormami de ) and a combination thereof.

Preferably, the thickener for the ion conducting layer is selected from the group consisting of polyethylene glycol (PEG), polypropylene glycol, polyethylene oxide (olyethylene) Oxide), polyether polyvinyl alcohol (polyvinyl a 1 coho 1 ), polymethy 1 methacrylate: polyacrylonitrile (polyacrylonitrile), polydimethyl methacrylate [poly ( N) , N-dimethylacrylamide ) ], poly[ 2 - ( 2 -methoxyethoxy) - ethoxy] phosphazene Cpoly [ 2 - ( 2 -methoxyethoxy ) - e th 0 X y 1 ph 0 s phazene, Poly(oxymethylene-oligooxyethylene) [poly

( 0 X y m e t h y 1 e ne-ol i go( oxyethylene) )] and the - combinations of these.

Preferably, the electrochromic device further comprises a reflective metal layer disposed on the first polymer substrate or the second polymer substrate.

The reflective metal layer may comprise any metal having photoreflective properties. Preferably, the reflective metal layer comprises a metal selected from the group consisting of silver, aluminum, and a combination thereof.

Optionally, the electrochromic device further comprises a protective layer disposed on the reflective metal layer, the purpose of which is to prevent the reflective metal layer from being scratched

Preferably, the protective layer contains a substance selected from the group consisting of silicon oxide (SiO ₂ ), titanium oxide (Ti0 ₂ ), aluminum oxide (A 1 ₂ 0 ₃ ), silicon nitride. ( J, epoxy resin ( ep 0 X y resin ) ^ acrylic resin

( acry 1 ic resin), urethane resi n, silicone resin ( si 1 i .cone resin ), parylene resin, polyimide, and a combination of the same.

Preferably, the electrochromic device further comprises a first polymer disposed on the first polymer a transparent protective layer on the substrate or on the second polymer substrate, the purpose of which is to protect the substrate

Preferably, the transparent protective layer comprises a group selected from the group consisting of oxidized laurel, titanium oxide, aluminum oxide, silicon nitride, epoxy resin, acrylic resin, urethane resin, and silicone resin. , a poly-p-xylene resin, a polyimine, and a combination thereof.

Preferably, the ion conducting layer is sandwiched between two mutually joined electrochromic layers and the auxiliary electrochromic layer. In a specific embodiment of the present invention, the electrochromic layer and the auxiliary electrochromic layer are bonded to each other by an adhesive layer to facilitate adhesion while improving the reliability and weather resistance of the entire device. .

The adhesive layer can be any adhesive material and can be patterned

(Pa 11 erned) printing or otherwise coating on the electrochromic layer or the auxiliary electrochromic layer. Preferably, the adhesive layer is composed of a substance selected from the group consisting of Made of: epoxy resin, acrylic resin, urethane resin silicone resin, poly-p-xylylene resin, polyimine, and a group of P

The first conductive layer and the second conductive layer, the electrochromic layer and the auxiliary electrochromic layer of the electrochromic device of the present invention can be prepared according to any known method, such as physical vapor deposition. Sol-gel method (s 01 - - ge 1 ), chemical solution deposition (chemical solution dep 0 siti 0 n ), chemical vapor deposition (chemical vapor depositi 0 n coating method, plasma-assisted chemical vapor deposition) ( ias ma ass isted chemical vapor deposition) method, electroplating (piating) fe, electroless plating (elcctroless lating) method and vacuum deposition (vacuum deposition) method, etc., another ij is as in the above-mentioned special cases lj case The methods described are hereby incorporated by reference.

When the electrochromic device of the present invention is used, the two conductive layers of the device are electrically connected to a power source, and the voltage is applied to cause an electrochromic effect. The power source is a DC power source. In addition to being directly processed into a subsequent product, the electrochromic device of the present invention has direct flexibility because of its flexibility. Apply to any object (such as directly attached to a window). In addition, when it is made into a light-reflecting flexible electrochromic device, it can be used in automotive rearview mirrors or other mirrors.

The foregoing and other technical aspects, features and functions of the present invention are assigned below

P Detailed description of the attached drawings will be clearly presented

Before the present invention is described in detail, it should be noted that similar elements in the following description are denoted by the same reference numerals.

1 Preparation of light penetrating flexible electrochromic device

Example 1

Referring to FIG. 3, Embodiment 1 of the flexible electrochromic device of the present invention comprises a first polymer substrate 1 made of polyethylene terephthalate, and a parallel with the first polymer substrate 1. a second polymer substrate 2 and an intermediate unit 3 made of polyethylene terephthalate at intervals, the intermediate unit 3 is oriented from the first polymer substrate 1 toward the second polymer substrate Included in sequence; a first conductive layer 3 1 , an electrochromic layer 3 2 , an ion conducting layer 3 3 and an adhesive layer 3 6 , an auxiliary electrochromic layer 3 made of vanadium oxide 4 and a second conductive layer 3 5 . The first conductive layer 3 1 and the second conductive layer 3 5 are all made of indium tin oxide, the electrochromic layer 3 2 is made of tungsten oxide, and the ion conductive layer 34 is made of carbonic acid. C. Ester, ester with a concentration of 1 M L, i C 1 0 , . and polyethylene glycol (1 will be referred to as

The P C - L i C I O 4 - P E G " ) is formed. The adhesive layer 3 6 is formed of an epoxy resin.

The light transmissive flexible electrochromic device of the first embodiment is prepared as follows: the first polymer substrate 1 and the second polymer substrate 2 having a thickness of 175 μm are respectively coated on the first polymer substrate 1 and the second polymer substrate 2 Layer of indium tin oxide, each forming a resistance value of 3

0 Ω 1 □ of the first conductive layer 3 1 and the second conductive layer 3 5 °, respectively, using a tungsten target and a vanadium target at room temperature and a pressure of 4 0 mt 0 rr " a sputter coating technique, the first conductive layer 3 1 is coated with a layer of tungsten oxide and the second conductive layer 3 5 is coated with a layer of vanadium oxide to form the electrochromic layer 3 2 . (The finished semi-finished product is expressed as "PET / IT0 / W0 ₃ ") and the auxiliary electrochromic layer 3 4 (the finished semi-finished product is expressed as "PET / IT0 / V ₂ 0 ₅ "). An epoxy resin is separately applied to the electrochromic layer 3 2 and the auxiliary electrochromic layer 3 4 by a dispenser, and a screen printing method is used. The above electrolyte is applied between the electrochromic layer 3 2 and the auxiliary electrochromic layer 34. Finally, the electrochromic layer 3 2 is combined with the auxiliary electrochromic layer 34 by applying pressure, and is cured by ultraviolet rays at room temperature to obtain the light-transmissive flexible method of the embodiment 1. The electrochromic device (sequentially stacked from top to bottom is PET / IT0 / W0 ₃ I PC-LiC10 ₄ -PEG IV ₂ 0 ₅ I ITO I PET ).

Trans mi ttance test:

First, the light-transmitting flexible electrochromic device of the embodiment 1 is bent at 90 ° (as shown in Fig. 4), and after being restored to the original state, the following test is performed: '

The first conductive layer ³¹ and the second conductive layer ³⁵ is connected to a DC voltage of 3 V, and then repeatedly and continuously through the + 3 V or - 3 V voltage (when fed - voltage at 3 V, the electroluminescent The color change device will change to a colored state, and when the voltage of + 3 V is applied, the electrochromic device will be converted into a decolored state), and at the wavelength of 65 nm, the ultraviolet light-visible spectrometer will be used ( UV-VIS spectroscope) The transmittance test of the electrochromic device of Example 1 was carried out, and the results obtained are shown in Fig. 5. As can be seen from Fig. 5, the transmittance changes from 72% to about 2 2% in about 15 seconds (the transmittance change value Δ Τ = the transmittance at the time of complete color removal - the transmittance at the time of complete coloring) 50%), and the change in the transmittance can be stably maintained with time, thereby demonstrating that the light-transmitting flexible electrochromic device of the embodiment 1 does have excellent light adjustment. degree.

2. Preparation of light-reflecting flexible electrochromic device: Example 2

The structure of the light-reflective flexible electrochromic device of the second embodiment is different from the light-transmissive flexible device of the embodiment 1 except that the material of the first conductive layer 31 is changed from indium tin oxide to silver. The structure of the color-changing device is the same, and the light-reflecting and squeezing electrochromic device is prepared by the same process (sequentially stacked from top to bottom as PET 1 Ag 1 wo _a , 1 PC-LiC10 ₄ - PEG 1 V ₂ 0 ₅ 1 IT01 PET ). Example 3

The structure of the light-reflective flexible electrochromic device of the embodiment 3 and the light-transmissive flexible electro-optic device of the embodiment 1 except that the material of the second conductive layer 35 is changed from indium tin oxide to silver The structure of the color change device is the same, and the light reflection flexible electrochromic device is made from top to bottom according to the same process. PET / IT0 / wo _{3 1} 1 PC- Li C10 ₄ -PEG 1 V ₂ 0 ₅ / 'Ag 1 PET ). Example 4

Referring to FIG. 6, in addition to a reflective metal layer disposed on the first polymer substrate 1 and made of silver, the remaining structure of the light-reflecting electrochromic device of the fourth embodiment is The light-transmissive flexible electrochromic device of Embodiment 1 has the same structure, and the light-reflecting flexible electrochromic device is manufactured by the same process (the top-down stacking is Ag 1 PET 1 IT0 1 wo ₃ 1

PC iCIO 4 - PEG 1 V ₂ 0 ₆ 1 ITO 1 PET ). Example 5

Referring to FIG. 7, the remaining structure of the light-reflecting flexible electrochromic device of the fifth embodiment is further except that the reflective metal layer 4 is formed on the first polymer substrate 2 and made of silver. The light-transmissive flexible electrochromic device of the embodiment 1 has the same structure, and the light-reflecting flexible electrochromic device is prepared by the same process (the top-down stacking is PET 1 IT0) / ' W0 ₃ 1

PC-LiC10, -PEG 1 V ₂ 0 ₅ 1 IT0 PET / Ag ). Reflectance test:

First, the light-reflecting flexible electrochromic device of the embodiment 5 is folded.

0 J After returning to the original state, the following test is performed: Connect the first conductive layer 3 1 and the first conductive layer 3 5 to a 3 V DC voltage and then repeatedly and sell the + 3 V or - 3 V voltage (when When the voltage of -3 V is applied, the electrochromic device changes to a colored state, and when the voltage of +3 V is applied, the electrochromic device changes to a decolored state), and at the same time, the first polymer The substrate 1 is provided with ultraviolet light having a wavelength of 65 nm, and the reflectivity of the reflectance test of the electrochromic device of the fifth embodiment is performed by using an ultraviolet-visible spectrometer as shown in FIG. , the reflectance changes from about 5 5 % to about 15 % in about 15 seconds (reflectance change value AR = reflection when completely decolored - reflection rate of full color when the color is 40%), and with time The change can stably maintain the reflectance change value, thereby demonstrating that the light-reflecting flexible electrochromic device of the embodiment 5 does have excellent light regulation.

Referring to FIG. 9, the remaining structure of the light-reflecting flexible electrochromic device of Embodiment 6 and the implementation thereof are provided except that a protective layer 5 is formed on the reflective metal layer 4 and made of silicon oxide. The light-reflecting flexible electrochromic deformation of Example 4 has the same structure, and the light-reflecting flexible electrochromic device is prepared by the same process (from top to bottom, sequentially stacked as Si0 ₂ / Ag / PET / IT0 I PC- LiC10 wide _{_{PEG / V 2 0 5 / ITO}} / PET) 0 embodiment Ί embodiment

Referring to FIG. 10, (3⁄4; further comprising a protective layer 5 disposed on the reflective metal layer 4 and made of silicon oxide, the light-reflecting flexible electrochromic device of the seventh embodiment The structure is the same as that of the light-reflecting flexible electrochromic device of the real 5, and the light-reflecting flexible electrochromic device is manufactured by the process (the second to the next are sequentially stacked as PET TO W0 PC) -LiC10 ₄ -PEG IV ₂ 0 TO PET A SiO Example 8

Referring to FIG. 11 , the rest of the light-reflecting electrochromic device of the embodiment 8 is provided except that a transparent protective layer 6 is formed on the second polymer substrate 2 and made of silicon oxide. The structure is the same as that of the light-reflecting flexible electrochromic device of the embodiment 6, and the light-reflecting and flexible electrochromic device is prepared by the same process (the top-down stack is sequentially stacked as Si0 ₂ / Ag / PET

1 IT01 1 PC-LiC10, PEG 1 V ₂ 0 ₅ I ITO I PET I Si0 ₂ ) Example 9

Referring to FIG. 12, the remaining structure of the light-reflecting flexible electrochromic device of the embodiment 9 is further except that a transparent protective layer 6 is formed on the first polymer substrate 1 and made of silicon oxide. The light-reflecting flexible electrochromic device is the same as that of the light-reflecting flexible electrochromic device of the first embodiment, and the light-reflecting and flexible electrochromic device is formed by the same process (sequentially stacked from top to bottom as S: : 1 PET 1 ITO

1 W0 ₃ 1 PC-Li C10 ₄ - -PEG 1 V ₂ 0 ₅ 1 IT0 1 PET 1 Ag 1 S i 0 _: o

As described above, the flexible electrochromic device of the present invention uses a flexible polymer material as a substrate and uses an inorganic metal oxide which is not affected by ultraviolet rays to form the electrochromic layer and is provided with the auxiliary. The electrochromic layer and the ion-conducting layer make the flexible electrochromic device of the invention have the advantages of better stability, easy control of coloring and decoloring state, and adjustable coloring depth, and can be made according to actual needs. Light-transmitting or light-reflecting flexible electrochromic device, which has good light regulation after bending, is particularly applicable to an energy-saving product having a curved surface such as automobile components (such as glass, skylight, backlight) Mirror), electronic paper, electronic product table

And smart windows, etc.

However, the above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent change and modification according to the scope of the present invention and the description of the invention are still white. Within the scope of the invention covered by the patent

Claims

Rights request

A sturdy electrochromic device characterized by comprising: a flexible first polymer substrate

a flexible first high molecular substrate disposed in parallel with the first m molecular substrate and

An intermediate unit disposed between the first molecular substrate and the first molecular substrate, and the intermediate unit is sequentially included by the first molecular substrate toward the second 13⁄4 molecular substrate: a first conductive layer, an electric Color change layer, an ion conductive layer, an auxiliary electrochromic layer and a "first conductive layer"

Wherein the electrochromic layer is made of a tungsten oxide oxidized by a metal oxide selected from the group consisting of: titanium oxide, cerium oxide, cerium oxide, and the like. The auxiliary electrochromic layer is made of a metal oxide selected from the group consisting of vanadium oxide, nickel oxide, chromium oxide, manganese oxide, iron oxide, copper oxide, cerium oxide, and the like. Wait

Group

The flexible electrochromic device according to claim 1, wherein the first polymer substrate and the first polymer substrate are respectively selected from a material group consisting of the following groups. Made of: polyethylene terephthalate, polycarbonate, acrylic, and a group of these

The flexible electrochromic device according to claim 1, wherein the first conductive layer and the first conductive layer respectively comprise a group selected from the group consisting of Metal oxides: oxidized 'tin, indium tin oxide, antimony tin oxide, antimony-doped tin oxide, antimony tin oxide, zinc oxide, and the like

A flexible electrochromic device according to claim 1, wherein the electrochromic layer is made of tungsten oxide.

5. The flexible electrochromic device according to claim 4, wherein the auxiliary electrochromic layer is made of vanadium oxide. The squeezing electrochromic device according to claim 1, wherein the meat conductive layer contains a lithium-containing salt, a dispersing agent, and a thickener.

The flexible electrochromic device according to claim 6, wherein the lithium-containing class is selected from the group consisting of lithium perchlorate and difluorochloride. Methane sulfonamide lithium lithium difluoromethane sulfonate, nonafluoro

, .

Lithium butyl sulfonate, lithium chloride, lithium octafluorophosphate, and the group of these

8. The flexible electrochromic device according to claim 6, wherein the dispersing agent is selected from the group consisting of: propylene carbonate, ethylene carbonate, γ - - Butyric acid: lactone ί, acetylephrine, methylformamide, and these groups

9. The flexible electrochromic device according to claim 6, wherein the thickener is selected from the group consisting of polyethanol, polypropanol, polyethylene oxide, Polyether, vinyl alcohol, polymethyl methacrylate, polyacrylonitrile, dimethyl methacrylate. Poly[ 2 - ( 2 - methoxyethoxy) - ethoxy] phosphazene, poly (oxymethylene-oligooxyethylene), and a group of P

The flexible electrochromic device according to claim 1, wherein the first conductive layer contains a metal selected from the group consisting of silver, aluminum, and the like. A set of the first conductive layer is a metal oxide selected from the group consisting of tin oxide, indium tin oxide, antimony tin oxide, fluorine-doped tin oxide, antimony tin oxide, zinc oxide. And a group of these

1 1 The flexible electrochromic device according to claim 1, wherein the first conductive layer contains a metal oxide selected from the group consisting of: tin oxide, Indium tin oxide, antimony tin oxide, tin oxide doped with fluorine, antimony tin oxide, zinc oxide, and a group of n, the first conductive layer is a metal containing a group selected from the group consisting of : silver, aluminum, and a group of these

1 2 The 电-type electrochromic device according to claim 1, The method further includes a reflective metal layer disposed on the first polymer substrate

The flexible electrochromic device according to claim 12, wherein the reflective metal layer comprises a metal selected from the group consisting of: silver, aluminum And a combination of these.

The flexible electrochromic device according to claim 12, further comprising a protective layer disposed on the reflective metal layer.

The flexible electrochromic device according to claim 14 , wherein the protective layer comprises a substance selected from the group consisting of: silicon oxide, oxidation Titanium, aluminum oxide, silicon nitride, epoxy resin, acrylic resin, urethane resin, silicone resin, polyparaxylene resin, polyimine, and a combination thereof.

The flexible electrochromic device according to claim 14 , further comprising a transparent protective layer disposed on the second polymer substrate

The flexible electrochromic device according to claim 16, wherein the transparent protective layer comprises a group selected from the group consisting of silicon oxide, titanium oxide, Alumina, silicon nitride, epoxy resin, acrylic resin, urethane resin, silicone resin, polyparaxylene resin, polyimine, and a combination thereof.

The flexible electrochromic device according to claim 1, further comprising a reflective metal layer disposed on the second polymer substrate

The flexible electrochromic device according to claim 18, wherein the reflective metal layer comprises a metal selected from the group consisting of: silver, aluminum And a combination of these.

The flexible electrochromic device according to claim 18, further comprising a protective layer disposed on the reflective metal layer.

The flexible electrochromic device according to claim 20, wherein the protective layer comprises one selected from the group consisting of Substances in the group: silicon oxide, titanium oxide, aluminum oxide, silicon nitride, epoxy resin, acrylic resin, urethane resin, silicone resin, polyparaxylene resin, polyimine and this a combination of the same.

The flexible electrochromic device according to claim 20, further comprising a transparent protective layer disposed on the first polymer substrate

The flexible electrochromic device according to claim 2, wherein the transparent protective layer comprises a group selected from the group consisting of silicon oxide, titanium oxide, Alumina, silicon nitride, epoxy resin, acrylic resin, urethane resin, silicone resin, polyparaxylene resin, polyimine, and a combination thereof.

2 . The flexible electrochromic device according to claim 1 , wherein the ion conductive layer is sandwiched between two mutually coupled electrochromic layers and the auxiliary electrochromic layer Between layers.

The flexible electrochromic device according to claim 24, wherein the electrochromic layer and the auxiliary electrochromic layer are coated by an adhesive layer. Four around and joined to each other.

The flexible electrochromic device according to claim 25, wherein the adhesive layer is made of a substance selected from the group consisting of: Epoxy resin, acrylic resin, urethane resin, silicone resin, polyparaxylene resin, polyimine, and the like