CN103186003A - Flexible organic electrochromic device and processing method thereof - Google Patents
Flexible organic electrochromic device and processing method thereof Download PDFInfo
- Publication number
- CN103186003A CN103186003A CN2011104486617A CN201110448661A CN103186003A CN 103186003 A CN103186003 A CN 103186003A CN 2011104486617 A CN2011104486617 A CN 2011104486617A CN 201110448661 A CN201110448661 A CN 201110448661A CN 103186003 A CN103186003 A CN 103186003A
- Authority
- CN
- China
- Prior art keywords
- organic electrochromic
- bendable
- transparent
- layer
- electrochromic layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention discloses a flexible organic electrochromic device and a processing method thereof. The electrochromic device mainly comprises a first transparent flexible substrate, a first transparent conducting layer, an organic electrochromic layer, a second transparent flexible substrate, a second transparent conducting layer, an auxiliary organic electrochromic layer and an electrolyte. A staggered, parallel and overlapped packing technique is adopted in the flexible organic electrochromic device, so that the required driving voltage can be lowered, the discoloration time is shortened, and the aim of flexible application is fulfilled.
Description
Technical field
The invention relates to a kind of electrochromic device and its manufacturing method thereof, more especially relevant for a kind of bendable organic electrochromic device and its manufacturing method thereof, by the encapsulation technology of staggered parallel crossover, this electrochromic device can reduce required driving voltage and shorten its light modulation time and bendable application is provided.
Background technology
Generally speaking, electrochromic device refers to a kind of when an electric field is provided, and produces electrochemical redox reaction, causes the change of light penetration characteristic, and then causes the device of change color.Wherein, this process is a reversible process, and when no extra electric field, this electrochromic material namely recovers primary characteristic.Utilize the characteristic of electrochromic material, can be made into the electrochromism display device.Electrochromic material can be applicable to various fields at present, for example: veil of vehicle mosaic glass (as vehicle window, skylight), building mosaic glass, display device, optical element, mirror body and electromagnetic wave irradiation etc., its function is to intercept effectively the interference of the external world's (as light, heat).Wherein, electrochromic material is classified as reduction colour generation material and oxidation colour generation material.Reduction colour generation material refers to generally comprise tungsten oxide because of electron gain colour generation person; Simultaneously, oxidation colour generation material refers to generally comprise nickel oxide and cobalt oxide because losing electronics colour generation person; Other electroluminescent materials that comprise inorganic, metal oxide are as Ir (OH) x, MoO
3, V
2O
5, TiO
2Etc..It should be noted that above-mentioned electroluminescent material all must can colorificly change in containing lithium ion or hydrionic electrolyte environment.
With reference to No. the 5th, 441,827, United States Patent (USP) notification number, it has disclosed a kind of device with high-level efficiency, high reaction rate, and the preparation of this device mainly is to have the membrane electrode surface of nano aperture, applies the organic purpurine compound of simple layer electrochemical activity.This device has utilized a lithium salts and organic solvent such as gamma butyrolactone, and (potpourri of γ-butyrolactone) and propylene carbonate (propylene carbonate) is as electrolyte.Yet this utilization contains organic solvent as electrolytical device, and shortcoming is that its quenching speed (quenching rate) is low, still ghost can occur behind quenching, and organic material decomposes in the circulation of development and quenching easily.Wherein, more because device uses the aqueous electrolyte contain organic solvent, therefore easier generation electrolyte volatilization and the shortcoming that exhausts, and electrolyte may come out by spill and leakage from device, and cause the problem of not environmental protection.Simultaneously, film shaped or that product is made the film external form is more infeasible.In addition, this patent also is not explained in detail the method for packing of last upper/lower electrode, so also influences the subsequent applications scope simultaneously.
Duty is event, the applicant is careful test and research, and spirit of working with perseverance, finally work out a kind of electrochromic device and manufacturing method thereof thereof, have the more advantage of lower driving voltage and light modulation time and apparent color, and provide wider subsequent applications scope by bendable design.
Summary of the invention
Fundamental purpose of the present invention is to propose a kind of bendable organic electrochromic device, has lower driving voltage and light modulation time, and provides wider subsequent applications scope by bendable design.
Another object of the present invention is to provide a kind of preparation method of bendable organic electrochromic device, under the condition by the encapsulation technology of the staggered parallel crossover of electrode, develop and a kind of driving voltage and electrochromic device of light modulation time of reducing.
For reaching above-mentioned purpose, the present invention proposes a kind of bendable organic electrochromic device, and it comprises: one first transparent bendable base material; One first transparency conducting layer; One organic electrochromic layer; One second transparent bendable base material; One second transparency conducting layer; One auxiliary organic electrochromic layer; One electrolyte.Wherein, this first transparency conducting layer is coated on the surface of this first bendable transparent base, forms one first transparent bendable conductive base; This organic electrochromic layer is coated on the surface of this first transparency conducting layer; This second transparency conducting layer is coated on the surface of this second transparent bendable base material, forms one second transparent bendable conductive base; Should assist the organic electrochromic layer, be coated on the surface of this second transparency conducting layer; And this electrolyte, mixed by an ionic liquid and a gum polymers, be filled in this first transparent bendable conductive base that contains this organic electrochromic layer and contain between this second transparent bendable conductive base of this auxiliary organic electrochromic layer.
For reaching another above-mentioned purpose, the present invention proposes a kind of manufacturing method thereof of bendable organic electrochromic device, and its step comprises: one first transparent bendable base material is provided; Deposit one first transparency conducting layer in the surface of this first transparent bendable base material, form one first transparent bendable conductive base; Deposit an organic electrochromic layer in the surface of this first transparency conducting layer; One second transparent bendable base material is provided; Deposit one second transparency conducting layer in the surface of this second transparent bendable base material, form one second transparent bendable conductive base; Deposition one auxiliary organic electrochromic layer is in the surface of this second transparency conducting layer; This first transparent bendable conductive base that will contain this organic electrochromic layer respectively and this second transparent bendable conductive base that contains this auxiliary organic electrochromic layer are with a staggered parallel method crossover, to form two groups of L type boundary lines, relative distance between the length of the two transparent bendable conductive bases of this behind the crossover and length is between 0.2 to 3 centimeter, and wide and wide relative distance is between 0.2 to 3 centimeter; Filling is assisted between the organic electrochromic layer in containing this organic electrochromic layer and being somebody's turn to do by the electrolyte that an ionic liquid and a gum polymers mix; Along these two groups of L type boundary lines, carry out the action of an encapsulation with an encapsulation agent; Wherein, the driving voltage of this electrochromic device is between 2 volts to 20 volts, and the light modulation time is between 30 milliseconds to 60 seconds.
According to a feature of the present invention, this the first transparent bendable conductive base that wherein contains this organic electrochromic layer is reserved a border scope with this second transparent bendable conductive base that contains this auxiliary organic electrochromic layer, and with a staggered parallel method crossover, the length of the two electrically conducting transparent base materials of this behind the crossover and length and wide and wide between relative distance be between 0.2 to 3 centimeter.
According to a feature of the present invention, wherein this organic electrochromic layer be to be selected from ethylidene dioxy thiophenols (polyethylenedioxythiophene), polyaniline (polyaniline) (PANI) with assisting the organic electrochromic layer, polypyrrole (polypyrrole), viologen (viologen), metal phthalocyanine complex (metallophthalocyanines), poly-(2,5-dimethoxy aniline) one of [poly (2,5-dimethoxyanaline)], pyrazoline (pyrazoline), tetrathiafulvalene (tetrathiafulvalene).
According to a feature of the present invention, the composite material of this electrolyte and PVB glue material (or other glue materials) wherein, but using method has:
One, directly coating (wire mark) heating, drying sclerosis again behind copolymers;
Two, will contain electrolytical glue material makes behind the film the suitable size of cutting and posts behind copolymers and add two copolymers of hot pressing through laminating machine again.
A kind of bendable organic electrochromic device of the present invention and manufacturing method thereof thereof have following effect:
1. the driving voltage of this bendable organic electrochromic device is between 2 volts to 20 volts, and the light modulation time is between 30 milliseconds to 60 seconds;
2. can reduce about 1/2～1/3 by the encapsulation technology of the staggered parallel crossover of electrode of the present invention driving voltage than conventional package mode, and reduce simultaneously its light modulation time;
3. can effectively increase ionic conduction speed by the encapsulation technology of the staggered parallel crossover of electrode of the present invention and the enforcement of organic electrochromic layer, and shorten and go/the painted time, and more color performance will be arranged;
4. by bendable organic electrochromic device of the present invention, can make open electric circuit memory a few hours, keep the transmission stationary state and must not do the correction of potential pulse.
For above-mentioned and other purposes of the present invention, feature and advantage can be become apparent, several preferred embodiments cited below particularly, and cooperate appended graphicly, elaborate.
Description of drawings
Fig. 1 is shown as a kind of bendable organic electrochromic device of the present invention;
Fig. 2 is shown as the preparation method of a kind of bendable organic electrochromic device of the present invention;
Fig. 3 is shown as the vertical view of a kind of bendable organic electrochromic device of the present invention.
Main Reference numeral
100 bendable organic electrochromic devices
110 first transparent bendable base materials
The length of 111 first transparent bendable base materials
112 first transparent bendable base materials wide
120 first transparency conducting layers
121 L type boundary lines
130 organic electrochromic layers
140 second transparent bendable base materials
The length of 141 second transparent bendable base materials
142 second transparent bendable base materials wide
150 second transparency conducting layers
151 L type boundary lines
160 auxiliary organic electrochromic layers
170 electrolyte
The preparation method's of 200 bendable organic electrochromic devices process flow diagram
Embodiment
Though the present invention can show as multi-form embodiment, but the accompanying drawing those shown and in expositor hereinafter for the present invention can preferred embodiment, and please to understand content disclosed herein be to be thought of as one example of the present invention, and be not that intention is in order to be limited to the present invention in diagram and/or the described specific embodiment.
Now please refer to Fig. 1, it is shown as the structural representation of a kind of bendable organic electrochromic device 100 of the present invention.This electrochromic device 100 mainly comprises: one first transparent bendable base material 110; One first transparency conducting layer 120; One organic electrochromic layer 130; One second transparent bendable base material 140; One second transparency conducting layer 150; One auxiliary organic electrochromic layer 160; One electrolyte 170.Wherein, this first transparency conducting layer 120 is coated on the surface of this first transparent bendable base material 110, forms one first transparent bendable conductive base; This organic electrochromic layer 130 is coated on the surface of this first transparency conducting layer 120; This second transparency conducting layer 150 is coated on the surface of this second transparent bendable base material 140, forms one second transparent bendable conductive base; Should assist organic electrochromic layer 160, be coated on the surface of this second transparency conducting layer 150; And this electrolyte 170, mixed by an ionic liquid and a gum polymers, be filled in this first transparent bendable conductive base that contains this organic electrochromic layer and contain between this second transparent bendable conductive base of this auxiliary organic electrochromic layer.Wherein, this first transparent bendable base material 110 is selected from flexible base plate with this second transparent bendable base material 140, this flexible base plate can be: poly-to benzene (polyethylene terephthatate), polycarbonate (polycarbonate), the modern hydrocarbon copolymerization (cycloolefin copolymers) of cyclenes, polystyrene (polystyrene), polyacrylate (polyacrylate), segmented copolymer (copolymers), and the scope of the length 111 of this first transparent bendable base material 110 and the length 141 of this second transparent bendable base material 140 is between 0.1 meter to 2 meters, and wide 112 and 142 scope is between 0.1 meter to 1.5 meters.The difference of its element is the conductive base difference used, if base material is all glass or bendable plastic plate, is the penetration element, can be applicable to intelligent window and filter, and the number of light penetration amount can be determined by the current potential of conductive base.If base material simultaneously is transparent conducting glass or bendable plastic plate, another side is the light tight base material with reflectivity properties, is reflecting element, can be applicable on rearview mirror or the display.
Now please refer to Fig. 2, it is shown as the manufacturing method thereof 200 of a kind of bendable organic electrochromic device of the present invention.It comprises following step:
Step 210: deposit one first transparency conducting layer 120 in the surface of this first transparent bendable base material 110, form one first transparent bendable conductive base;
Step 220: deposit an organic electrochromic layer 130 in the surface of this first transparency conducting layer 120;
Step 230: deposit one second transparency conducting layer 150 in the surface of this second transparent bendable base material 140, form one second transparent bendable conductive base;
Step 240: deposition one auxiliary organic electrochromic layer 160 is in the surface of this second transparency conducting layer 150;
Step 250: this first transparent bendable conductive base that will contain this organic electrochromic layer respectively and this second transparent bendable conductive base that contains this auxiliary organic electrochromic layer are with a staggered parallel method crossover, to form two groups of L type boundary lines 121 and 151.The length of the two transparent bendable conductive bases of this behind the crossover and length and wide and wide between relative distance be between 0.5 to 3 centimeter;
Step 260: fill an electrolyte 170 in this first transparent bendable conductive base 110 that contains this organic electrochromic layer 130 and contain between this second transparent bendable conductive base 140 of this auxiliary organic electrochromic layer 160;
Step 270: along these two groups of L type boundary lines 121 and 151, carry out the action of an encapsulation with an encapsulation agent.Carry out an action that encapsulates with an encapsulation agent along two groups of L type boundary lines 121 and 151 of abc and adc.
Wherein, this first transparency conducting layer 120 is the roles that play the part of conductive electrode in this bendable organic electrochromic device 100 with this second transparency conducting layer 150, provide the variable color process required electric current, therefore must adopt the transparent conductive material that has high penetration and high electrical conductivity concurrently.So, in the present invention, this transparency conducting layer be selected from tin indium oxide (Indium Tin Oxide, ITO), aluminum zinc oxide (Aluminum Zinc Oxide, AZO), the fluorine doped tin oxide film (Fluorine Tin Oxide, one of FTO).Preferably, again because therefore fluorine doped tin oxide film (FTO) acid and alkali-resistance, heat-resisting, moisture-proof and the film forming raw material is cheap and production cost is low, be to use the fluorine doped tin oxide film in the present invention.In addition, this first transparency conducting layer 120 is to be selected from one of sputtering method, vapour deposition method, electrochemical plating, the long-pending method in chemical gaseous phase Shen, sol-gel process, spraying cracking process, infusion process, electrochemical process with the deposition process of this second transparency conducting layer 150, and the thickness of film forming is between 50 nanometer to 300 nanometers.
Its material of this electric driven color-changing part is extensive, can be divided into inorganic oxide and organic material etc. haply, and inorganic material is modal to be tungstic acid (WO
3) and nickel oxide (NiO) etc., organic material then comprises four big series: (1) viologens (2) conducting polymers (3) metallopolymers (4) metallophthaloyanines.Electronic product in the following daily life will develop towards slimming, and the product that light weight and volume are little will develop successively, and the organic electrochromic material will be a nova of attracting attention in light, thin, short, the little design wind of this ripple.
The off-color material that the traditional electrical photochromic device adopts is inorganic oxide series, for example: WO
3, NiO, IrO
2Deng, yet its response time is slower, is applied to faster that display is inadequate, so the organic electrochromic material is good selection.
The organic electrochromic material is as follows compared with the advantage that other electrochromic material has:
(1) low cost
The organic electrochromic material is that cost of manufacture is cheaper than the advantage that traditional inorganic material has on making.In making the electric driven color-changing part aspect, the organic electrochromic material can utilize sputtering method, vapour deposition method, electrochemical plating, chemical vapour deposition technique, sol-gel process, spraying cracking process, infusion process, electrochemical process one of them, form thin film uniformly from the teeth outwards, vacuum evaporation mode with traditional inorganic oxide, cost of manufacture is cheaper, and production process is also oversimplified.
(2) the quick and good optical characteristics of change color
The organic electrochromic material can significantly increase the surface area that contact with electrolyte for making electric driven color-changing part via the change of production process to form cellular structure, makes ion embed or embedding goes out faster, the time of shortening change color.Another advantage then is to utilize electrolyte can efficiently allow ion produce displacement, so that element has faster and uniform change color, the electric driven color-changing part during for the big chi of making is a big advantage.
(3) good cyclical stability (operation lifetime)
The deflectionization of structure is another advantage of organic electrochromic material.Electric driven color-changing part is actually a sandwich structure, the pattern of whole element is with regard to the hull cell of a similar chargeable/discharge, when color when coloring or bleaching change, ion just embeds or embedding goes out electrochromic material, electrochromic material will present periodic expansion with electrolytical phase, if the crystalline network of material is firm situation, the process of charge/discharge will be destroyed and electrolytical interface, and this will be a main cause that influences the element operation life-span.Utilize organic electrochromic material and polyelectrolyte to make electric driven color-changing part and will significantly promote operation lifetime, because of the organic electrochromic material more many than the structurally flexible of inorganic material, the structure of organic electrochromic material will have buffering and the phenomenon that expands when charge/discharge, make whole destruction significantly reduce to carry and give birth to its life-span.
(4) modifiable structure is made to reach the element of suitable character
At the improvement of polythiophene variable color speed, add different functional groups to reach required characteristic and change color.In addition, because the diversity of organic electrochromic material structure, therefore the change fitness of processing procedure is also higher, utilize polypyrrole to carry out the design of processing procedure, polypyrrole since on high molecular main chain adjoining carbon have singly-bound and two keys are staggered, cause the generation that can be with is arranged and the appearance that has light.Polypyrrole has many application, for example: solar cell, thin film transistor (TFT) and chemical sensor etc.Polypyrrole changes down in different current potentials under the system of electrochemical treatment, and discovery is in oxidation and go back the change that ortho states has color, that is to say that it has electrochromic behavior.
(5) color diversity
The organic electrochromic material has the various character of color usually, is example with the polyphenyl saddle, and its color can be from transparent green and the blueness of changing to.Change in color can stop via the control of current potential certain period, so follow-up making electric driven color-changing part, will present the diversity of color.The organic electrochromic material will make electric driven color-changing part present more various variation by the modification of structure.
The substrate of bendable organic electrochromic device adopts high molecular plastic base, for example poly-to benzene (polyethylene terephthatate), polycarbonate (polycarbonate), the modern hydrocarbon copolymerization (cycloolefin copolymers) of cyclenes, polystyrene (polystyrene), polyacrylate (polyacrylate), segmented copolymer (copolymers) one of them.Electrolytical selection aspect can be selected the ion of less size usually, so that the ion rate travel is very fast, and makes electric driven color-changing part present response time faster, and ion commonly used is hydrogen ion (H
+) and lithium ion (Li
+).Bendable organic electrochromic element will make element slimming and processing procedure oversimplify, and for example the traditional electrical photochromic device is to adopt ito glass, and glass is because the restriction of shape and breaking easily has influence on its practicality.Make bendable electric driven color-changing part, selecting for use of polyelectrolyte is just extremely important, macromolecule commonly used is divided into two big classes according to the ion that uses, and the first kind is for using hydrionic polyelectrolyte, and representational macromolecule is polyethylene oxide (PEO).Another kind of for using the polyelectrolyte of lithium ion, representational macromolecule be poly (methylmethacrylate) (PMMA), the demand of the polyelectrolyte of this two type is to have high ionic conductance, low crystallization degree and the higher free degree of ion under room temperature state.The selection of polyelectrolyte will be to make electric driven color-changing part and influence the important selection of electrochromic property to consider.
In the present invention, this organic electrochromic layer 130 normally is selected from ethylidene dioxy thiophenols (polyethylenedioxythiophene), polyaniline (polyaniline) (PANI), polypyrrole (polypyrrole), viologen (viologen), metal phthalocyanine complex (metallophthalocyanines), poly-(2,5-dimethoxy aniline) one of [poly (2,5-dimethoxyanaline)], pyrazoline (pyrazoline), tetrathiafulvalene (tetrathiafulvalene).
Wherein, preferably, attract most attention at present and widely research the organic electrochromic material be polyaniline (PANI), pyrazoline, poly (2,5-dimethoxyanaline) (PDMA) is because it has high coloration efficiency (Coloration efficiency), reversibility is good, relative price is low, longest-lived and advantage such as nontoxic.Increase poly (2,5-dimethoxyanaline) in the method for the solubleness of (PDMA), utilize official's energy acidic group (functional acid) doping poly (2,5-dimethoxyanaline) research of (PDMA) is pointed out, not only promote to some extent for the macromolecule dissolution degree, electrical conductivity also increases to some extent simultaneously.Sense acidic group commonly used has para-toluene-sulfonic acid (TSA), dodecyl benzene sulfonic acid (DBSA), and camphor sulfonic acid (CSA) etc.In addition, the modification method of high polymer main chain is also commonly used, utilizes the ring substitutive derivative, or the N-substitutive derivative carry out polymerization or copolymerization modify poly (2, the 5-dimethoxyanaline) structure of (PDMA).(2,5-dimethoxyanaline) (PDMA) derivant firm degree that can reduce main chain to be increasing solubleness, but its relative electrical conductivity significantly reduces for these poly.The puratized agricultural spray derivant (2 that replaces with two methoxyls on the phenyl ring, 5-dimethoxyanaline), through aggregating into poly (2,5-dimethoxyanaline) after (PDMA), its solubleness significantly promotes, and in the electrical conductivity puratized agricultural spray derivant near the polyphenyl ammonium.Therefore (2,5-dimethoxyanaline) (PDMA) variable color speed is very quick for poly.
Poly (2,5-dimethoxyanaline) (PDMA) and derivant thereof can have two tangible redox couples in sulfuric acid or aqueous hydrochloric acid solution, comprise that leucoemeraldine is oxidizing to emeraldine and emeraldine is reduced to the pernigraniline form.Yet, outside these two redox couples, still might have other redox couple, for example: be embedded in the oligomer of macromolecular structure inside or the redox couple of macromolecule deterioration.
Through a reversible electrochemical reaction thus in oxidation state and go back do between the ortho states repeatedly discolor and painted.After stopping externally-applied potential, ion with the utmost point slowly method of diffusion leave, form the distinctive memory effect of electrochromism element, need impose externally-applied potential at any time with respect to other products, have energy-saving advantages.
On the other hand, this auxiliary photochromic layer 160 can be general electrode or another kind of electrochromism material, is used for strengthening color or permeability variations.The electric driven color-changing part of forming when the collocation of auxiliary electrode and another kind of working electrode is called complementary electrochromism element (Complementary electrochromic device).If electrochromic layer is to go back the painted material of ortho states, auxiliary electrode layer then need use the painted material of oxidation state.Therefore, the two poles of the earth are painted or discolor simultaneously during the energising of complementary electrochromism element, have high coloration efficiency and bigger advantages such as optical density (OD) difference.And should normally be selected from ethylidene dioxy thiophenols (polyethylenedioxythiophene), polyaniline (polyaniline) (PANI) by auxiliary organic electrochromic layer 160, polypyrrole (polypyrrole), viologen (viologen), metal phthalocyanine complex (metallophthalocyanines), poly-(2,5-dimethoxy aniline) one of [poly (2,5-dimethoxyanaline)], pyrazoline (pyrazoline), tetrathiafulvalene (tetrathiafulvalene).Preferably be polyaniline (PANI), pyrazoline, poly (2,5-dimethoxyanaline) (PDMA) and tetrathiafulvalene (tetrathiafulvalene), it be the organic electroluminescence look change material of cheap, high-level efficiency and high stability.
In a specific example of the present invention, this organic electrochromic layer is that (2,5-dimethoxyanaline) (PDMA) is made, and this auxiliary organic electrochromic layer also is that (2,5-dimethoxyanaline) (PDMA) is made by poly by poly.Wherein, this organic electrochromic layer 130 is to be selected from one of sputtering method, vapour deposition method, electrochemical plating, the long-pending method in chemical gaseous phase Shen, sol-gel process, spraying cracking process, infusion process, electrochemical process with the deposition process that should assist organic electrochromic layer 160, and the thickness of film forming is between 80 nanometer to 600 nanometers.
This first transparent bendable conductive base 110 that contains this organic electrochromic layer 130 is reserved a border scope with this second transparent bendable conductive base 140 that contains this auxiliary organic electrochromic layer 160, and with a staggered parallel method crossover, to form two groups of L type boundary lines 121 and 151.The length of the two transparent bendable conductive bases of this behind the crossover and length and wide and wide between relative distance be between 0.5 to 3 centimeter, as shown in Figure 3.Because this kind crossover method can make the usable area of the first transparent bendable conductive base 110 and the second transparent bendable conductive base 140 increase and then the operating voltage of integral member is reduced.
170 layers in electrolyte in the present invention, its function provides and conducting ion gives electrochromic material, so must store a large amount of kations, and can rapid diffusion enter photochromic layer, therefore make it to react colorific variation, good ionic conduction layer should have high electronic values and good ionic conduction ability on using.Wherein, electrolyte is selected colloidal state for use in the present invention.The early stage liquid electrolyte that adopts is quite inconvenient in the element encapsulation, and the doubt of spill and leakage is arranged, so the colloidal electrolytes that use are formed bendable electric driven color-changing part more now.Yet, known solid electrolyte (LiNbO for example
3Or Ta
2O
5) need just can finish painted under the high voltage or discolor being continuously applied, and the time that spends is longer, can effectively increase ionic conduction speed and be gluey dielectric substrate, and shorten and go/the painted time, and only need apply a low voltage simultaneously and just can finish and discolor or colored state.
Wherein, the colloidal electrolyte among the present invention 170 is mixed by an ionic liquid and a gum polymers.Generally speaking, this ionic liquid is made up of a metal cation and a metalloid anion, example hydrochloric acid (NaCl) aqueous solution, and more specifically, at room temperature the ionic liquid that exists with liquid state is referred to as RTIL (room temperature ionic liquid).Wherein, because ionic liquid is not had a volatility, therefore do not have vapour pressure, and ionic conductance is also high; In particular, because ionic liquid has high polarity, so fine for the dissolving power of inorganic or organic compound, and the characteristic under liquid can present under vast temperature range, therefore can be applicable to the number of chemical field, comprise crystallography, isolation technics and galvanochemistry.In addition, because the low-symmetry of ionic liquid, more weak and the CHARGE DISTRIBUTION of inter-molecular attraction is in characteristics such as kations, so have low melting point, even ionic liquid is not had toxicity, nonflammable, the temperature stability height, its physicochemical characteristic is better than having the solvent of environmental protection characteristics, therefore can replace the organic solvent of traditional tool toxicity.Physicochemical characteristic comprises and can be rendered as liquid state under vast temperature range that high solvent characteristic and formation is the ability of reciprocity bond not.In practicality, the bendable organic electrochromic device of the electrolyte 170 that this ionic liquid that the present invention uses and this gum polymers mix provides following advantage:
(1) gelated electrolyte can keep ionic liquid, and solves the problem of electrolyte spill and leakage; (2) because the ion concentration of the electrolyte 170 of ion liquid polymerization and tradition are height based on the electrolyte of organic solvent, so the development of organic electrochromic element and device/quenching speed is higher.Relatively organic electrochromic element of the present invention and device and one use the electrochromic device of liquid electrolyte, and its reaction rate is equally matched, because the ionic conductance of ionic liquid is up to 10
-3～10
-6Between the S/cm.In addition, organic electrochromic element of the present invention more provides an electrochromic device with high memory effect (Memory Effect) with device; (3) ionic liquid has maximum electrochemical voltage scope (electrochemical window), also therefore utilizes organic solvent to compare for main electrolyte with one, and electrolytical decomposition possibility is lower among the present invention; (4) use a more stable ionic liquid because of apparatus of the present invention, therefore can reduce the subsidiary reaction of electrochromic device; (5) ion colloid polyeletrolyte does not have vapor pressure, therefore not with electrolytical volatilization with exhaust relevant problem.In addition, utilize lithium or hydrogen to carry out the phenomenon of the color development/quenching of organic electrochromic device, can influence because of the ion concentration in ionic conductance and the electrolyte 170; Generally speaking, ionic conductance is to measure the mobile degree of ion in electrolyte 170 solution.Therefore, the ion concentration in solution viscosity and the solution all can influence ionic conductance.Viscosity descends in solution, and ion can move freely, and causes ionic conductance to rise; And when the increase of effects of ion concentration, amount of ions will increase, and causes ionic conductance to increase relatively; The traditional liquid electrolyte has than low-viscosity, so its ion concentration is about 10
-2～10
-4Between the S/cm; And the electrolyte 170 that this ionic liquid that the present invention uses and this gum polymers mix, its ionic conductance is about 10
-3～10
-6Between the S/cm.In the present invention, the kation in this ionic liquid and negative ion are all unrestricted.On the other hand, this gum polymers is to be selected from polymethylmethacrylate (polymethyl methacrylate, PMMA), polyvinylidene fluoride (polyvinylidene difluoride, PVDF), Polyvinylchloride (polyvinyl chloride, PVC), polyoxyethylene (polyethylene oxide, PEO) and poly hydroxy ethyl acrylate (polyhydroxyethyl methacrylate, PHEMA), Ethylene vinyl accetate copolymer (Ethylene vinyl accetate copolymer, EVA), polyvinyl alcohol (PVA) (Polyvinyl alcohol, PVA), polyphenylene oxide (polyphenylene oxide), polyglycol (polyethylene glycol), polypropylene glycol (polypropylene glycol), trifluoromethanesulfonic acid lithium (lithium triflate), one of lithium perchlorate (lithium perchlorate).
The composite material of electrolyte and PVB glue material (or other glue materials), but using method has:
One, directly coating (wire mark) heating, drying sclerosis again behind copolymers;
Two, will contain electrolytical glue material makes behind the film the suitable size of cutting and posts behind copolymers and add two copolymers of hot pressing through laminating machine again.
When using bendable organic electrochromic device 100 of the present invention, be that the first bendable conductive base and the second bendable conductive base with this device electrically connects with a direct current power supply, again by feeding voltage, can make the electrochromic effect of generation.Wherein, can make the driving voltage of this bendable organic electrochromic device 100 by this encapsulation technology of interlocking parallel method crossover is between 2 volts to 20 volts, and the light modulation time is between 30 milliseconds to 60 seconds.
In one embodiment, copolymers (1.4 meters * 1.1 meters) is at first handled through degreasing agent, removed surface and oil contaminant, again through the not residual degreasing agent in washing relief copolymers surface, keep clean, carry out cleaning treatment with utmost point dilute hydrochloric acid aqueous solution on this copolymers surface more afterwards, clean to remove unnecessary utmost point dilute hydrochloric acid aqueous solution with clear water again, at last copolymers is plated the FTO film of 200 nanometers with the method for sputter.On the other hand, forming a bed thickness with electro-plating method in FTO copolymers surface is polyaniline (PANI) working electrode of 300nm; It is the polyaniline (PANI) of 300nm that another counter electrode also forms a thickness with said method in FTO copolymers surface; Working electrode and counter electrode are reserved outside the bounds zone one, with a staggered parallel method crossover, the length of the two transparent bendable conductive bases of this behind the crossover and length and wide and wide between relative distance be between 0.5 centimeter.At last, encapsulate with an encapsulation agent that contains beaded glass gap along its corner, do not contain electrolytical bendable organic electrochromic device to form one.
Then, prepare one and contain the electrolyte that ionic liquid and a gum polymers mix.Wherein this ionic liquid is the 1M LiClO of lithium salts
4, and the ionic liquid (wherein EMIM is ethyl-methyl imidazol ion [ethyl methyl imidazolium]) that is mixed with [EMIM] [BF4]; And this gum polymers be Ethylene vinyl accetate copolymer (Ethylene vinyl accetate copolymer, EVA).This electrolyte is injected the bendable organic electrochromic device that contains inorganic, metal oxide polyaniline (PANI)/polyaniline (PANI) electrode that above-mentioned preparation is finished.Wherein, the ionic conductance of the gum polymers electrolyte of formation at room temperature is about 10
-3S/cm.Wherein, when electrolyte and glue material mix, be to use direct coating (wire mark) heating, drying sclerosis again behind copolymers.At last, two electrodes and a direct current power supply are electrically connected, again by the voltage that feeds 20 volts, can make the effect that produces electrochromism, and the light modulation time is 0.5 second.Wherein, the electrochromic device finished of the preparation color purple that develops, penetrance is about 20%; When quenching, this electrochromic device is yellow color, and penetrance is 30%.In addition, because above-mentioned bendable organic electrochromic device uses gelated electrolyte, therefore do not have to surpass more than 90 hours because the problem of electrolyte spill and leakage or volatilization provides an excellent memory effect simultaneously.
Claims (12)
1. a bendable organic electrochromic device is characterized in that, comprises:
One first transparent bendable base material;
One first transparency conducting layer is coated on a surface of this first transparent bendable base material, forms one first transparent bendable conductive base;
One organic electrochromic layer is coated on a surface of this first transparency conducting layer;
One second transparent bendable base material;
One second transparency conducting layer is coated on a surface of this second transparent bendable base material, forms one second transparent bendable conductive base;
One assists the organic electrochromic layer, is coated on a surface of this second transparency conducting layer; And
One electrolyte is mixed by an ionic liquid and a gum polymers, is filled in this organic electrochromic layer and should assists between the organic electrochromic layer;
Wherein, this first transparent bendable base material and this second transparent bendable base material are all rectangular structure, and its length range is between being between 0.1 meter to 3 meters, and the scope of its width is between 0.1 meter to 2 meters;
The driving voltage of this organic electrochromic device is between 2 volts to 20 volts, and the light modulation time of this organic electrochromic device is between 30 milliseconds to 60 seconds; And
This organic electrochromic layer be to be selected from ethylidene dioxy thiophenols (polyethylenedioxythiophene), polyaniline (polyaniline) (PANI) with assisting the organic electrochromic layer, polypyrrole (polypyrrole), viologen (viologen), metal phthalocyanine complex (metallophthalocyanines), poly-(2,5-dimethoxy aniline) one of [poly (2,5-dimethoxyanaline)], pyrazoline (pyrazoline), tetrathiafulvalene (tetrathiafulvalene).
2. bendable organic electrochromic device according to claim 1, it is characterized in that, this first transparent bendable base material and this second transparent bendable base material are to be selected to gather benzene (polyethylene terephthatate), polycarbonate (polycarbonate), the modern hydrocarbon copolymerization (cycloolefin copolymers) of cyclenes, polystyrene (polystyrene), polyacrylate (polyacrylate), one of segmented copolymer (copolymers).
3. bendable organic electrochromic device according to claim 1 is characterized in that, this organic electrochromic layer is poly-(2,5-dimethoxy aniline) [poly (2,5-dimethoxyanaline)], and should auxiliary organic electrochromic layer be tetrathiafulvalene.
4. bendable organic electrochromic device according to claim 1 is characterized in that, this organic electrochromic layer further comprised with assisting the organic electrochromic layer: a light absorber, a light stabilizer and a temperature stability agent.
5. the manufacturing method thereof of a bendable organic electrochromic device is characterized in that, its step comprises:
(a) provide one first transparent bendable base material;
(b) deposition one first transparency conducting layer forms one first transparent bendable conductive base in a surface of this first transparent bendable base material;
(c) deposition one organic electrochromic layer is in a surface of this first transparency conducting layer;
(d) provide one second transparent bendable base material;
(e) deposition one second transparency conducting layer forms one second transparent bendable conductive base in a surface of this second transparent bendable base material;
(f) deposition one auxiliary organic electrochromic layer is in a surface of this second transparency conducting layer;
(g) this first transparent bendable conductive base that will contain this organic electrochromic layer respectively and this second transparent bendable conductive base that contains this auxiliary organic electrochromic layer are with a staggered parallel method crossover, to form two groups of L type boundary lines, relative distance between the length of the two transparent bendable conductive bases of this behind the crossover and length is between 0.5 to 3 centimeter, and wide and wide relative distance is between 0.5 to 3 centimeter;
(h) filling an electrolyte that is mixed by an ionic liquid and a gum polymers assists between the organic electrochromic layer in containing this organic electrochromic layer and being somebody's turn to do;
(i) along these two groups of L type boundary lines, carry out the action of an encapsulation with an encapsulation agent;
Wherein, the driving voltage of this organic electrochromic device is between 2 volts to 20 volts, and the light modulation time is between 30 milliseconds to 60 seconds;
Wherein this organic electrochromic layer be to be selected from ethylidene dioxy thiophenols (polyethylenedioxythiophene), polyaniline (polyaniline) (PANI) with assisting the organic electrochromic layer, polypyrrole (polypyrrole), viologen (viologen), metal phthalocyanine complex (metallophthalocyanines), poly-(2,5-dimethoxy aniline) one of [poly (2,5-dimethoxyanaline)], pyrazoline (pyrazoline), tetrathiafulvalene (tetrathiafulvalene).
6. manufacturing method thereof according to claim 5, it is characterized in that the scope of this first transparent base of step (a) and step (d) and the length of this second transparent base is between 0.1 meter to 3 meters and the scope of width is between 0.1 meter to 1.5 meters.
7. manufacturing method thereof according to claim 5 is characterized in that, step (b) is to be selected from one of tin indium oxide (ITO), aluminum zinc oxide (AZO), fluorine doped tin oxide film (FTO) with this first transparency conducting layer and second transparency conducting layer of step (e).
8. manufacturing method thereof according to claim 5, it is characterized in that step (b) is to be selected from one of sputtering method, vapour deposition method, electrochemical plating, the long-pending method in chemical gaseous phase Shen, sol-gel process, spraying cracking process, infusion process, electrochemical process with this first transparency conducting layer of step (e) and the deposition process of this second transparency conducting layer.
9. manufacturing method thereof according to claim 5, it is characterized in that step (c) is to be selected from one of sputtering method, vapour deposition method, electrochemical plating, the long-pending method in chemical gaseous phase Shen, sol-gel process, spraying cracking process, infusion process, electrochemical process with this organic electrochromic layer of step (f) with the deposition process that should assist organic photochromic layer.
10. manufacturing method thereof according to claim 5, it is characterized in that step (c) is that poly-(2,5-dimethoxy aniline) [poly (2 with this organic electrochromic layer of step (f), 5-dimethoxyanaline)], and should auxiliary organic electrochromic layer be tetrathiafulvalene.
11. manufacturing method thereof according to claim 5 is characterized in that, when this ionic liquid mixes with this gum polymers, is to use direct coating or wire mark to have after electromechanics causes the transparent bendable conductive base of photochromic layer heating, drying sclerosis again in this.
12. manufacturing method thereof according to claim 5, it is characterized in that, when this ionic liquid mixes with this gum polymers, be after containing electrolytical glue material and making the film shape, post behind this transparent bendable conductive base with this organic electrochromic layer, be pressed on these two through laminating machine heating again and have the transparent bendable conductive base that electromechanics causes photochromic layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104486617A CN103186003A (en) | 2011-12-28 | 2011-12-28 | Flexible organic electrochromic device and processing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104486617A CN103186003A (en) | 2011-12-28 | 2011-12-28 | Flexible organic electrochromic device and processing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103186003A true CN103186003A (en) | 2013-07-03 |
Family
ID=48677255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104486617A Pending CN103186003A (en) | 2011-12-28 | 2011-12-28 | Flexible organic electrochromic device and processing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103186003A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630731A (en) * | 2015-03-09 | 2015-05-20 | 哈尔滨工业大学 | Preparation method for electrochromic device |
| JP2016095503A (en) * | 2014-11-06 | 2016-05-26 | キヤノン株式会社 | Organic electrochromic element, optical filter, lens unit, and imaging apparatus |
| CN108549185A (en) * | 2018-06-01 | 2018-09-18 | Oppo广东移动通信有限公司 | Shell and preparation method, electronic equipment |
| CN109283704A (en) * | 2017-07-21 | 2019-01-29 | 韩国电子通信研究院 | Reversible electrochemical mirror |
| CN110361902A (en) * | 2018-04-10 | 2019-10-22 | 香港纺织及成衣研发中心有限公司 | Electric driven color-changing part, device, product and production and preparation method thereof |
| CN112327555A (en) * | 2020-11-20 | 2021-02-05 | 浙江工业大学 | Electrochromic device, preparation method thereof and application of electrochromic device in intelligent window |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002287172A (en) * | 2001-03-26 | 2002-10-03 | Sony Corp | Electrochromic display element and electrochromic display device |
| CN1990820A (en) * | 2005-12-30 | 2007-07-04 | 财团法人工业技术研究院 | Electrochromism film |
| WO2008049275A1 (en) * | 2006-10-25 | 2008-05-02 | Feng Chia University | Flexible electromic apparatus |
| CN101852960A (en) * | 2010-05-14 | 2010-10-06 | 马鞍山市盛宁高分子材料科技有限公司 | Full-solid state macromolecule controllable electrochromism flexible film device and manufacturing method thereof |
| CN102109725A (en) * | 2011-01-24 | 2011-06-29 | 电子科技大学 | Electrochromic device and preparation method thereof |
-
2011
- 2011-12-28 CN CN2011104486617A patent/CN103186003A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002287172A (en) * | 2001-03-26 | 2002-10-03 | Sony Corp | Electrochromic display element and electrochromic display device |
| CN1990820A (en) * | 2005-12-30 | 2007-07-04 | 财团法人工业技术研究院 | Electrochromism film |
| WO2008049275A1 (en) * | 2006-10-25 | 2008-05-02 | Feng Chia University | Flexible electromic apparatus |
| CN101852960A (en) * | 2010-05-14 | 2010-10-06 | 马鞍山市盛宁高分子材料科技有限公司 | Full-solid state macromolecule controllable electrochromism flexible film device and manufacturing method thereof |
| CN102109725A (en) * | 2011-01-24 | 2011-06-29 | 电子科技大学 | Electrochromic device and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016095503A (en) * | 2014-11-06 | 2016-05-26 | キヤノン株式会社 | Organic electrochromic element, optical filter, lens unit, and imaging apparatus |
| CN104630731A (en) * | 2015-03-09 | 2015-05-20 | 哈尔滨工业大学 | Preparation method for electrochromic device |
| CN109283704A (en) * | 2017-07-21 | 2019-01-29 | 韩国电子通信研究院 | Reversible electrochemical mirror |
| CN109283704B (en) * | 2017-07-21 | 2022-05-10 | 韩国电子通信研究院 | Reversible electrochemical mirror |
| CN110361902A (en) * | 2018-04-10 | 2019-10-22 | 香港纺织及成衣研发中心有限公司 | Electric driven color-changing part, device, product and production and preparation method thereof |
| CN108549185A (en) * | 2018-06-01 | 2018-09-18 | Oppo广东移动通信有限公司 | Shell and preparation method, electronic equipment |
| CN112327555A (en) * | 2020-11-20 | 2021-02-05 | 浙江工业大学 | Electrochromic device, preparation method thereof and application of electrochromic device in intelligent window |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9778534B2 (en) | Chromatic systems | |
| CN202563220U (en) | Electrochromic device | |
| Yun et al. | Dual-function electrochromic supercapacitors displaying real-time capacity in color | |
| CN103582844B (en) | Stable electrochromic module | |
| Oh et al. | Voltage-tunable multicolor, sub-1.5 V, flexible electrochromic devices based on ion gels | |
| Moon et al. | Multicolored, low-power, flexible electrochromic devices based on ion gels | |
| TWI385814B (en) | Photoelectrochromics device and method of manufacturing the same | |
| US10545387B2 (en) | Electrochromic device for applying voltage to electrodes | |
| CN103186003A (en) | Flexible organic electrochromic device and processing method thereof | |
| CN102759835B (en) | Fiber-shaped flexible electrochromic device and preparation method thereof | |
| CN103135306A (en) | Electrochromism assembly provided with composite electrochromism materials | |
| Ma et al. | Using room temperature ionic liquid to fabricate PEDOT/TiO2 nanocomposite electrode-based electrochromic devices with enhanced long-term stability | |
| WO2007008978A2 (en) | Electrochromic devices utilizing very low band gap conjugated polymers: preparation and use | |
| JP2004526195A (en) | Electrochromic device | |
| CN101930142A (en) | Photoelectrochromic element and manufacturing method thereof | |
| US9535304B2 (en) | Stable electrochromic module | |
| CN112540488B (en) | Electrochromic device capable of being cut at will and application | |
| CN105372896A (en) | Preparation of solid electrolyte electrochromic flexible device based on conductive polymer | |
| EP3635761B1 (en) | Multifunctional solid-state devices for solar control, photovoltaic conversion and artificial lighting | |
| CN202404340U (en) | Electrochromic component | |
| da Costa Rios et al. | Electrochromic devices based on poly (3-methylthiophene) and various secondary electrochromic materials | |
| Primiceri et al. | Enhanced Durability of an All-Solid-State WO3 Based Electrochromic Device on a Single Substrate by Using a Complementary Anodically Coloring Poly (o-ethoxyaniline) | |
| JP2001188264A (en) | Electrochromic display device | |
| CN103135305A (en) | Electrochromism device provided with porous structure and manufacture procedure method thereof | |
| TWI450009B (en) | Electrochromic device and method of manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130703 |