CN107032637A - A kind of preparation method of compound electrochromic membrane - Google Patents

A kind of preparation method of compound electrochromic membrane Download PDF

Info

Publication number
CN107032637A
CN107032637A CN201710355014.9A CN201710355014A CN107032637A CN 107032637 A CN107032637 A CN 107032637A CN 201710355014 A CN201710355014 A CN 201710355014A CN 107032637 A CN107032637 A CN 107032637A
Authority
CN
China
Prior art keywords
electrochromic
preparation
oxidation
solution
compound
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.)
Granted
Application number
CN201710355014.9A
Other languages
Chinese (zh)
Other versions
CN107032637B (en
Inventor
熊善新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian University of Science and Technology
Original Assignee
Xian University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Xian University of Science and Technology filed Critical Xian University of Science and Technology
Priority to CN201710355014.9A priority Critical patent/CN107032637B/en
Publication of CN107032637A publication Critical patent/CN107032637A/en
Application granted granted Critical
Publication of CN107032637B publication Critical patent/CN107032637B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C03C2217/231—In2O3/SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • C03C2217/241—Doped oxides with halides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/251—Al, Cu, Mg or noble metals
    • C03C2217/252—Al
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/251—Al, Cu, Mg or noble metals
    • C03C2217/254—Noble metals
    • C03C2217/255—Au
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/251—Al, Cu, Mg or noble metals
    • C03C2217/254—Noble metals
    • C03C2217/256—Ag
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/112—Deposition methods from solutions or suspensions by spraying
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/119—Deposition methods from solutions or suspensions by printing

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention discloses a kind of preparation method of compound electrochromic membrane, this method is：Added water preparation polymeric reaction solution by monomer, dopant acid and oxidation-reduction indicator first, and be combined oxidation-reduction indicator and conducting polymer using in situ chemical oxidative polymerization method, conducting polymer/oxidation-reduction indicator composite electrochromic solution is prepared, the solution is finally built into electrochomeric films by spin coating, spraying, lifting or printing-filming mode on transparent conducting glass or perforated membrane.The present invention improves the discoloration of conducting polymer electrochromic material using chromogenic reaction of the oxidation-reduction indicator in conducting polymer electrochromic process, and by using different macromolecular dopant acids during chemical polymerization in the original location, obtaining has water miscible composite electrochromic solution, final to obtain the good compound electrochromic membrane of electrochromic property.

Description

A kind of preparation method of compound electrochromic membrane
Technical field
The invention belongs to electrochomeric films technical field, and in particular to a kind of preparation side of compound electrochromic membrane Method.
Background technology
Electrochromic material can less driving voltage (<Reversible optical change is realized under 3V), and is widely used In fields such as smart window, display, military camouflage, infrared emanation modulation, automobile anti-dazzle back vision mirror and information storages.Conduction is poly- Compound has reversible redox reaction characteristic, and its band gap size and optical property can occur reversible under action of alternative electric field Change, and as most study a class electrochromic material.Compared with inorganic electrochromic material, conducting polymer is electroluminescent Off-color material is in machinability, the selection of color, have larger advantage in devices light, flexibility and cost, still, its Still there are larger room for promotion, the electrochromism of especially single conducting polymer in terms of the richness and contrast of color It can not still meet the demand of practical application.Accordingly, it would be desirable to explore a kind of by conducting polymer and other increase colour change functions Material is combined, and is further improved the contrast and various colors degree of its electrochromic material, is expanded its application field.
The content of the invention
The technical problems to be solved by the invention are compound electroluminescent there is provided one kind for above-mentioned the deficiencies in the prior art The preparation method of optically variable films.The preparation method is aobvious in conducting polymer electrochromic process using oxidation-reduction indicator Colour response improves the discoloration of conducting polymer electrochromic material, and by being added during chemical polymerization in the original location Dopant acid is to obtain with water miscible composite electrochromic solution, eventually through spin coating, spraying, lifting or printing-filming mode The good compound electrochromic membrane of electrochromic property is obtained, and the preparation method filming performance is good.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of preparation of compound electrochromic membrane Method, it is characterised in that this method comprises the following steps：
Step 1: preparing polymeric reaction solution：Being added water by monomer, dopant acid and oxidation-reduction indicator, it is anti-to be configured to polymerization The concentration for answering monomer in solution, the polymeric reaction solution is 0.01mol/L~5mol/L, and the concentration of dopant acid is 0.01mol/ L~5mol/L, the concentration of oxidation-reduction indicator is 0.0001mol/L~0.5mol/L；
Step 2: in situ chemical oxidative polymerization reacts：Polymeric reaction solution described in step one is placed in cold bath, treated When the temperature of polymeric reaction solution is reduced to 0 DEG C, initiator is added by several times and triggers in situ chemical oxidative polymerization to react, reaction 12h~ Stop after 24h, obtain conducting polymer/oxidation-reduction indicator composite electrochromic solution；Chemical oxidising polymerisation is anti-in the original location Polymeric reaction solution is persistently stirred during answering, the speed of stirring is not less than 100r/min；
The mol ratio of initiator described in step 2 and monomer described in step one is (0.5~2)：1；
Step 3: film forming：By the conducting polymer obtained in step 2/oxidation-reduction indicator composite electrochromic solution Thick conducting polymer/the oxidations of 50nm~1000nm are formed in substrate by the film build method of spin coating, spraying, lifting or printing Reduce indicator compound electrochromic membrane.
The preparation method of above-mentioned a kind of compound electrochromic membrane, it is characterised in that monomer described in step one is benzene Amine, anil, pyrroles, azole derivatives, thiophene or thiophene derivant.
The preparation method of above-mentioned a kind of compound electrochromic membrane, it is characterised in that dopant acid is described in step one DBSA or polystyrolsulfon acid.
A kind of preparation method of above-mentioned compound electrochromic membrane, it is characterised in that redox described in step one Indicator is methylene blue, diphenylamine sulfonic acid sodium salt, erioglaucine A, phosphorus ferrosin ferrous iron or N-Phenylanthranilic acid.
The preparation method of above-mentioned a kind of compound electrochromic membrane, it is characterised in that initiator is described in step 2 Ammonium persulfate, ferric sulfate or iron chloride, when initiator is ferric sulfate or iron chloride, after in situ chemical oxidative polymerization reaction terminates Iron ion, which is removed, through dialysis obtains conducting polymer/oxidation-reduction indicator composite electrochromic solution.
A kind of preparation method of above-mentioned compound electrochromic membrane, it is characterised in that initiator described in step 2 with The mol ratio of monomer is 1：1.
The preparation method of above-mentioned a kind of compound electrochromic membrane, it is characterised in that substrate is described in step 3 Bright electro-conductive glass.
The preparation method of above-mentioned a kind of compound electrochromic membrane, it is characterised in that the transparent conducting glass is ITO Electro-conductive glass, AZO electro-conductive glass or FTO electro-conductive glass.
The preparation method of above-mentioned a kind of compound electrochromic membrane, it is characterised in that substrate described in step 3 is tool There is the porous substrate of metal film.
The preparation method of above-mentioned a kind of compound electrochromic membrane, it is characterised in that the metal film is golden film, silverskin Or aluminium film.
The present invention has advantages below compared with prior art：
1st, because oxidation-reduction indicator has reversible oxidation-reduction process, it can be presented in different redox states Go out different colours, and be commonly used for the terminal of redox reaction in determination solution.Due to the molecular weight of oxidation-reduction indicator It is relatively small, there is high sensitivity when redox state changes, the color change being exceedingly fast can be presented in minimum content. But because it is soluble small molecule, it is impossible in transparent conductive electrode or reflective electrode surface film forming, so it is difficult to directly work Used for electrochromic material.And the electrochromic process of conducting polymer is substantially exactly conducting polymer under alternating electric field Reversible redox reaction, the present invention oxidation-reduction indicator is incorporated into conductive polymer matrix, redox indicate Agent also can show color change in conducting polymer electrochromic process.Under same voltage, if redox is indicated Agent is identical with the color of conducting polymer, then can improve the contrast of conducting polymer electrochromic material；If redox Indicator is different from the color that conducting polymer is presented, and can also enrich the color of conducting polymer electrochromic material.The present invention The conducting polymer of preparation/oxidation-reduction indicator composite electrochromic material can improve the electroluminescent of conducting polymer from many aspects Discoloration, can further improve its electrochromic property, expand its application field.
2nd, the dopant acid of macromolecular is used during chemical polymerization in the original location of the invention, makes to be led after polymerisation Electric polymer/oxidation-reduction indicator composite electrochromic solution has water solubility, is easy to the later stage using conventional spin coating, spray Apply, lifting or printing-filming mode build electrochomeric films on transparent conducting glass or perforated membrane, and filming performance is good.
Technical scheme is described in further detail below by drawings and examples.
Brief description of the drawings
Fig. 1 is electrically conductive polyaniline/diphenylamine sulfonic acid sodium salt compound electrochromic membrane of the preparation of the embodiment of the present invention 1 in difference Visible absorption curve under voltage.
Fig. 2 is that visible ray of the electrically conductive polyaniline electrochomeric films of comparative example 1 of the present invention preparation under different voltages is inhaled Receive curve.
Fig. 3 is conductive poly- (3- pyrrol-carboxylic acids)/N-Phenylanthranilic acid composite electrochromic prepared by the embodiment of the present invention 3 Near infrared light reflectivity curve of the film under different voltages.
Fig. 4 is conductive poly- (3- pyrrol-carboxylic acids) electrochomeric films of comparative example 3 of the present invention preparation under different voltages Near infrared light reflectivity curve.
Embodiment
Embodiment 1
The preparation method of the electrically conductive polyaniline of the present embodiment/diphenylamine sulfonic acid sodium salt compound electrochromic membrane is：
Step 1: preparing polymeric reaction solution：Being added water by monomer, dopant acid and oxidation-reduction indicator, it is anti-to be configured to polymerization The concentration for answering monomer in solution, the polymeric reaction solution is 0.5mol/L, and the concentration of dopant acid is 0.5mol/L, redox The concentration of indicator is 0.005mol/L；The monomer is aniline；The dopant acid is polystyrolsulfon acid；The redox Indicator is diphenylamine sulfonic acid sodium salt；
Step 2: in situ chemical oxidative polymerization reacts：Polymeric reaction solution described in step one is placed in cold bath, treated When the temperature of polymeric reaction solution is reduced to 0 DEG C, divides 3 times and add initiator per minor tick 15min and trigger in situ chemical oxidation to gather Stop after closing reaction, reaction 18h, obtain electrically conductive polyaniline/diphenylamine sulfonic acid sodium salt composite electrochromic solution；Chemical oxygen in the original location Change and polymeric reaction solution is persistently stirred in polymerization process, the speed of stirring is 200r/min；The initiator and monomer Mol ratio be 1：1；The initiator is ammonium persulfate；
Step 3: the electrically conductive polyaniline obtained in step 2/diphenylamine sulfonic acid sodium salt composite electrochromic solution is passed through into rotation It is thin that the film build method of painting forms the thick electrically conductive polyaniline/diphenylamine sulfonic acid sodium salt composite electrochromics of 220nm on ITO electro-conductive glass Film, forms the photochromic layer of transmission-type electrochromic device；The rotating speed of the spin-coating film is 1000r/min, and spin-coating time is 1min。
Comparative example 1
The preparation method of the electrically conductive polyaniline electrochomeric films of this comparative example is：
Step 1: preparing polymeric reaction solution：Added water by monomer and dopant acid and be configured to polymeric reaction solution, the polymerization The concentration of monomer is 0.5mol/L in reaction solution, and the concentration of dopant acid is 0.5mol/L；The monomer is aniline；The doping Acid is polystyrolsulfon acid；
Step 2: in situ chemical oxidative polymerization reacts：Polymeric reaction solution described in step one is placed in cold bath, treated When the temperature of polymeric reaction solution is reduced to 0 DEG C, point 3 times and every minor tick 15min addition initiator initiated polymerizations, reaction Stop polymerization after 18h, obtain conductive polyaniline solution；Polymeric reaction solution is held in chemical oxidising polymerisation course of reaction in the original location Continuous stirring, stir speed (S.S.) is 200r/min；The mol ratio of the initiator and monomer is 1：1；The initiator is ammonium persulfate；
Step 3: by the conductive polyaniline solution obtained in step 2 by the film build method of spin coating in ITO electro-conductive glass Electrically conductive polyaniline electrochomeric films thick upper formation 220nm, form the photochromic layer of transmission-type electrochromic device；The rotation The rotating speed for applying film forming is 950r/min, and spin-coating time is 1min.
Fig. 1 is electrically conductive polyaniline/diphenylamine sulfonic acid sodium salt compound electrochromic membrane arrow along along figure prepared by the present embodiment 1 Visible absorption of the direction under -0.8V, -0.6V, -0.4V, -0.2V, 0V, 0.2V, 0.4V, 0.6V and 0.8V voltage is bent Line；Fig. 2 be comparative example 1 prepare electrically conductive polyaniline electrochomeric films along along figure the direction of arrow in -0.8V, -0.6V, - Knowable to visible absorption curve under 0.4V, -0.2V, 0V, 0.2V, 0.4V, 0.6V and 0.8V voltage, comparison diagram 1 and Fig. 2, The contrast of electrically conductive polyaniline/diphenylamine sulfonic acid sodium salt compound electrochromic membrane prepared by embodiment 1 is 0.902, compared to right The 0.503 of electrically conductive polyaniline electrochomeric films prepared by ratio 1, which has, to be greatly enhanced, and illustrates electrically conductive polyaniline/diphenylamines The electrochromic property of sodium sulfonate compound electrochromic membrane is more preferable.
Embodiment 2
The preparation of conductive poly- (3,4- Ethylenedioxy Thiophenes)/erioglaucine A compound electrochromic membranes of the present embodiment Method is：
Step 1: preparing polymeric reaction solution：Being added water by monomer, dopant acid and oxidation-reduction indicator, it is anti-to be configured to polymerization The concentration for answering monomer in solution, the polymeric reaction solution is 0.1mol/L, and the concentration of dopant acid is 0.1mol/L, redox The concentration of indicator is 0.001mol/L；The monomer is 3,4- Ethylenedioxy Thiophenes；The dopant acid is polystyrene sulphur Acid；The oxidation-reduction indicator is erioglaucine A；
Step 2: in situ chemical oxidative polymerization reacts：Polymeric reaction solution described in step one is placed in cold bath, treated When polymeric reaction solution temperature is reduced to 0 DEG C, point 3 times and every minor tick 15min addition initiator initiated polymerizations react 18h Stop polymerization afterwards, obtained after going iron ions through dialysis conductive poly- (3,4- Ethylenedioxy Thiophene)/erioglaucine A be combined it is electroluminescent Electrochromic solution；Polymeric reaction solution is persistently stirred in chemical oxidising polymerisation course of reaction in the original location, the speed of stirring is 100r/ Min, the mol ratio of the initiator and monomer is 1：1；The initiator is ferric sulfate；
Step 3: by conductive poly- (3,4- the Ethylenedioxy Thiophenes)/erioglaucine A compound electric mutagens obtained in step 2 Color solution forms thick conductive poly- (the 3,4- ethylenedioxy thiophenes of 50nm by the film build method of lifting on FTO electro-conductive glass Fen)/erioglaucine A compound electrochromic membranes, form the photochromic layer of transmission-type electrochromic device；The pulling film forming side The pull rate of method is 3mm/min, and membrane formation times are 2 times.
Comparative example 2
The preparation method of conductive poly- (3,4- Ethylenedioxy Thiophenes) electrochomeric films of this comparative example is：
Step 1: preparing polymeric reaction solution：Added water by monomer and dopant acid and be configured to polymeric reaction solution, the polymerization The concentration of monomer is 0.1mol/L in reaction solution, and the concentration of dopant acid is 0.1mol/L；The monomer is the sub- second dioxies of 3,4- Base thiophene；The dopant acid is polystyrolsulfon acid；
Step 2: in situ chemical oxidative polymerization reacts：Polymeric reaction solution described in step one is placed in cold bath, treated When polymeric reaction solution temperature is reduced to 0 DEG C, point 3 times and every minor tick 15min addition initiator initiated polymerizations react 18h Stop polymerization afterwards, go iron ions to obtain conductive poly- (3,4- Ethylenedioxy Thiophene) solution through dialysis；Chemical oxidation in the original location Polymeric reaction solution is persistently stirred in polymerization process, the speed of stirring is 100r/min, the initiator and monomer Mol ratio is 1：1；The initiator is ferric sulfate；
Step 3: the film forming side that conductive poly- (3,4- Ethylenedioxy Thiophenes) solution obtained in step 2 is passed through into lifting Method forms thick conductive poly- (3, the 4- Ethylenedioxy Thiophene) electrochomeric films of 50nm on FTO electro-conductive glass, forms Penetrate the photochromic layer of formula electrochromic device；The pull rate of the pulling film forming method is 4mm/min, and membrane formation times are 2 times.
According to visible absorbance test of the electrochomeric films under different voltages, poly- (3,4- Asias prepared by embodiment 2 Ethylenedioxy thiophene) contrasts of/erioglaucine A compound electrochromic membranes is 0.623, compared to poly- (3,4- sub- second dioxies Base thiophene) electrochomeric films 0.448 are greatly increased, are taken on a red color additionally, due to erioglaucine A in oxidation state, And poly- (3,4- Ethylenedioxy Thiophene) is in colourless in oxidation state, during voltage is from negative be changed into just, poly- (3,4- sub- second Propylenedioxythiophene)/erioglaucine A compound electrochromic membranes are showed by dark blue to red change, and electrochromic property is obtained To improve, color is more enriched.
Embodiment 3
The preparation method of conductive poly- (3- the pyrrol-carboxylic acids)/N-Phenylanthranilic acid compound electrochromic membrane of the present embodiment For：
Step 1: preparing polymeric reaction solution：Being added water by monomer, dopant acid and oxidation-reduction indicator, it is anti-to be configured to polymerization The concentration for answering monomer in solution, the polymeric reaction solution is 0.2mol/L, and the concentration of dopant acid is 0.2mol/L, redox The concentration of indicator is 0.001mol/L；The monomer is 3- pyrrol-carboxylic acids；The dopant acid is DBSA；It is described Oxidation-reduction indicator is N-Phenylanthranilic acid；
Step 2: in situ chemical oxidative polymerization reacts：Polymeric reaction solution described in step one is placed in cold bath, treated When polymeric reaction solution temperature is reduced to 0 DEG C, point 3 times and every minor tick 15min addition initiator initiated polymerizations react 24h Stop polymerization afterwards, conductive poly- (3- pyrrol-carboxylic acids)/N-Phenylanthranilic acid compound electric mutagens are obtained after going iron ions through dialysis Color solution；Polymeric reaction solution is persistently stirred in chemical oxidising polymerisation course of reaction in the original location, the speed of stirring is not less than 150r/min；The mol ratio of the initiator and monomer is 1：1；The initiator is iron chloride；
Step 3: by conductive poly- (3- the pyrrol-carboxylic acids)/N-Phenylanthranilic acid composite electrochromic obtained in step 2 Solution forms 1000nm thick conductive poly- (3- pyrrol-carboxylic acids)/adjacent anilino- by the film build method of spraying process in porous golden film Benzoic acid compound electrochromic membrane, forms the photochromic layer of reflecting type electrochromic device；The air pressure of the spraying membrane formation process For 0.3MPa, the distance between nozzle and porous golden film are 30cm, and spraying number of times is 3 times.
Comparative example 3
The preparation method of conductive poly- (3- pyrrol-carboxylic acids) electrochomeric films of this comparative example is：
Step 1: preparing polymeric reaction solution：Added water by monomer and dopant acid and be configured to polymeric reaction solution, the polymerization The concentration of monomer is 0.2mol/L in reaction solution, and the concentration of dopant acid is 0.2mol/L, and the monomer is 3- pyrrol-carboxylic acids；Institute Dopant acid is stated for DBSA；
Step 2: in situ chemical oxidative polymerization reacts：Polymeric reaction solution described in step one is placed in cold bath, treated When polymeric reaction solution temperature is reduced to 0 DEG C, point 3 times and every minor tick 15min addition initiator initiated polymerizations react 24h Stop polymerization afterwards, conductive poly- (3- pyrrol-carboxylic acids) solution is obtained after going iron ions through dialysis；Chemical oxidising polymerisation is anti-in the original location Polymeric reaction solution is persistently stirred during answering, the speed of stirring is not less than 150r/min；The initiator and monomer rub You are than being 1：1；The initiator is iron chloride；
Step 3: by conductive poly- (3- pyrrol-carboxylic acids) solution obtained in step 2 by the film build method of spraying process many Thick conductive poly- (3- pyrrol-carboxylic acids) electrochomeric films of 1000nm are formed in the golden film of hole, reflecting type electrochromic device is formd Photochromic layer；The air pressure of the spraying membrane formation process is 0.2MPa, and the distance between nozzle and porous golden film are 20cm, spray number of times For 3 times.
Fig. 3 is conductive poly- (3- pyrrol-carboxylic acids)/N-Phenylanthranilic acid compound electrochromic membrane edge prepared by embodiment 3 Near infrared light reflectivity curve of the direction of arrow under 0.6V, 0.4V, 0V, -0.4V, -0.6V and -0.8V voltage in figure；Fig. 4 is Comparative example 3 prepare conductive poly- (3- pyrrol-carboxylic acids) electrochomeric films along along figure the direction of arrow in 0.6V, 0.4V, 0.2V, Near infrared light reflectivity curve under 0V, -0.4V, -0.6V and -0.8V voltage, poly- (3- pyrrol-carboxylic acids) prepared by embodiment 3/ The contrast of N-Phenylanthranilic acid compound electrochromic membrane is 57.2% (in terms of at 1600nm wavelength), compared to comparative example 48.1% (in terms of at 1600nm wavelength) of 3 poly- (3- pyrrol-carboxylic acids) electrochomeric films prepared is greatly increased, Simultaneously because the introducing of N-Phenylanthranilic acid, poly- (3- pyrrol-carboxylic acids)/N-Phenylanthranilic acid composite electrochromic material becomes The wave-length coverage covered during color is wider.
Embodiment 4
The preparation method of conductive poly- (aminoanisole)/methylene blue compound electrochromic membrane of the present embodiment is：
Step 1: preparing polymeric reaction solution：Being added water by monomer, dopant acid and oxidation-reduction indicator, it is anti-to be configured to polymerization The concentration for answering monomer in solution, the polymeric reaction solution is 0.01mol/L, and the concentration of dopant acid is 0.01mol/L, and oxidation is also The concentration of former indicator is 0.0001mol/L；The monomer is aminoanisole；The dopant acid is DBSA； The oxidation-reduction indicator is methylene blue；
Step 2: in situ chemical oxidative polymerization reacts：Polymeric reaction solution described in step one is placed in cold bath, treated When polymeric reaction solution temperature is reduced to 0 DEG C, point 3 times and every minor tick 15min addition initiator initiated polymerizations react 12h Stop polymerization afterwards, obtain conductive poly- (aminoanisole)/methylene blue composite electrochromic solution；Chemical oxidising polymerisation in the original location Polymeric reaction solution is persistently stirred in course of reaction, the speed of stirring is 200r/min；Mole of the initiator and monomer Than for 0.5：1；The initiator is ammonium persulfate；
Step 3: conductive poly- (the aminoanisole)/methylene blue composite electrochromic solution obtained in step 2 is logical Cross printing film build method is formed in porous aluminium 300nm thickness conductive poly- (aminoanisole)/methylene blue be combined it is electroluminescent Optically variable films, forms the photochromic layer of reflecting type electrochromic device；The printing-filming method is with the poly- (methoxybenzene of conduction Amine)/methylene blue composite electrochromic solution be ink, with ink-jet printer in porous aluminium printing-filming, printing times For 3 times.
The contrast of poly- (the aminoanisole)/methylene blue compound electrochromic membrane of conduction manufactured in the present embodiment is 43% (in terms of at 1600nm wavelength).Contrast compared to conductive poly- (aminoanisole) electrochomeric films is high, shows to lead The electrochromic property of voltolisation (aminoanisole)/methylene blue compound electrochromic membrane is more excellent.
Embodiment 5
The preparation method of the ferrous compound electrochromic membrane of the polypyrrole of the present embodiment/phosphorus ferrosin is：
Step 1: preparing polymeric reaction solution：Being added water by monomer, dopant acid and oxidation-reduction indicator, it is anti-to be configured to polymerization The concentration for answering monomer in solution, the polymeric reaction solution is 5mol/L, and the concentration of dopant acid is 5mol/L, and redox is indicated The concentration of agent is 0.5mol/L；The monomer is pyrroles；The dopant acid is DBSA；The redox is indicated Agent is that phosphorus ferrosin is ferrous；
Step 2: in situ chemical oxidative polymerization reacts：Polymeric reaction solution described in step one is placed in cold bath, treated When polymeric reaction solution temperature is reduced to 0 DEG C, point 3 times and every minor tick 15min addition initiator initiated polymerizations react 12h Stop polymerization afterwards, the ferrous composite electrochromic solution of electric polypyrrole/phosphorus ferrosin is obtained after going iron ions through dialysis；In original Polymeric reaction solution is persistently stirred in the chemical oxidising polymerisation course of reaction of position, the speed of stirring is 200r/min；It is described to trigger The mol ratio of agent and monomer is 2：1；The initiator is ferric sulfate；
Step 3: the ferrous composite electrochromic solution of the electric polypyrrole obtained in step 2/phosphorus ferrosin is passed through into spray The film build method of painting forms the ferrous compound electrochromic membrane of the thick electric polypyrroles of 400nm/phosphorus ferrosin on porous silverskin, Form the photochromic layer of reflecting type electrochromic device；The air pressure of the spraying membrane formation process is 0.4MPa, nozzle and porous golden film Distance is 25cm, and spraying number of times is 2 times.
The contrast of the ferrous compound electrochromic membrane of electric polypyrrole manufactured in the present embodiment/phosphorus ferrosin is 39% (in terms of at 1600nm wavelength), the contrast compared to electric polypyrrole electrochomeric films is high, shows electric polypyrrole/phosphorus two The electrochromic property of the luxuriant and rich with fragrance ferrous compound electrochromic membrane of nitrogen is more excellent.
Embodiment 6
The preparation method of the conductive polythiophene of the present embodiment/erioglaucine A compound electrochromic membranes is：
Step 1: preparing polymeric reaction solution：Being added water by monomer, dopant acid and oxidation-reduction indicator, it is anti-to be configured to polymerization The concentration for answering monomer in solution, the polymeric reaction solution is 1mol/L, and the concentration of dopant acid is 1mol/L, and redox is indicated The concentration of agent is 0.05mol/L；The monomer is thiophene；The dopant acid is DBSA；The redox refers to It is erioglaucine A to show agent；
Step 2: in situ chemical oxidative polymerization reacts：Polymeric reaction solution described in step one is placed in cold bath, treated When polymeric reaction solution temperature is reduced to 0 DEG C, point 3 times and every minor tick 15min addition initiator initiated polymerizations react 12h Stop polymerization afterwards, go iron ions to obtain conductive polythiophene/erioglaucine A composite electrochromic solution through dialysis；Change in the original location Polymeric reaction solution is persistently stirred during oxidative polymerization, the speed of stirring is 200r/min；The initiator with The mol ratio of monomer is 2：1；The initiator is ferric sulfate；
Step 3: the conductive polythiophene obtained in step 2/erioglaucine A composite electrochromic solution is passed through into spin coating Film build method forms the thick conductive polythiophene/erioglaucine A compound electrochromic membranes of 120nm on AZO electro-conductive glass, is formed The photochromic layer of transmission-type electrochromic device；The rotating speed of the spin-coating film is 1600r/min, and spin-coating time is 2min.
The contrast of conductive polythiophene manufactured in the present embodiment/erioglaucine A compound electrochromic membranes is 0.334, phase Contrast than conductive polythiophene electrochomeric films is high, shows conductive polythiophene/erioglaucine A compound electrochromic membranes Electrochromic property it is more excellent.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill Any simple modification, change and equivalence change that art is substantially made to above example, still fall within technical solution of the present invention Protection domain in.

Claims (10)

1. a kind of preparation method of compound electrochromic membrane, it is characterised in that this method comprises the following steps：
Step 1: preparing polymeric reaction solution：Being added water by monomer, dopant acid and oxidation-reduction indicator, it is molten to be configured to polymerisation The concentration of monomer is 0.01mol/L~5mol/L in liquid, the polymeric reaction solution, the concentration of dopant acid for 0.01mol/L~ 5mol/L, the concentration of oxidation-reduction indicator is 0.0001mol/L~0.5mol/L；
Step 2: in situ chemical oxidative polymerization reacts：Polymeric reaction solution described in step one is placed in cold bath, it is to be polymerized When the temperature of reaction solution is reduced to 0 DEG C, initiator is added by several times and is triggered after in situ chemical oxidative polymerization reaction, reaction 12h~24h Terminate reaction, obtain conducting polymer/oxidation-reduction indicator composite electrochromic solution；Chemical oxidising polymerisation reacts in the original location During polymeric reaction solution is persistently stirred, the speed of stirring is not less than 100r/min；
The mol ratio of initiator described in step 2 and monomer described in step one is (0.5~2)：1；
Step 3: film forming：The conducting polymer obtained in step 2/oxidation-reduction indicator composite electrochromic solution is passed through The film build method of spin coating, spraying, lifting or printing forms the thick conducting polymer/redox of 50nm~1000nm in substrate Indicator compound electrochromic membrane.
2. a kind of preparation method of compound electrochromic membrane according to claim 1, it is characterised in that institute in step one Monomer is stated for aniline, anil, pyrroles, azole derivatives, thiophene or thiophene derivant.
3. a kind of preparation method of compound electrochromic membrane according to claim 1, it is characterised in that institute in step one Dopant acid is stated for DBSA or polystyrolsulfon acid.
4. a kind of preparation method of compound electrochromic membrane according to claim 1, it is characterised in that institute in step one It is methylene blue, diphenylamine sulfonic acid sodium salt, erioglaucine A, the ferrous or adjacent anilino- benzene first of phosphorus ferrosin to state oxidation-reduction indicator Acid.
5. a kind of preparation method of compound electrochromic membrane according to claim 1, it is characterised in that institute in step 2 Initiator is stated for ammonium persulfate, ferric sulfate or iron chloride, when initiator is ferric sulfate or iron chloride, in situ chemical oxidative polymerization Reaction removes iron ion through dialysis after terminating and obtains conducting polymer/oxidation-reduction indicator composite electrochromic solution.
6. a kind of preparation method of compound electrochromic membrane according to claim 1, it is characterised in that institute in step 2 The mol ratio for stating initiator and monomer described in step one is 1：1.
7. a kind of preparation method of compound electrochromic membrane according to claim 1, it is characterised in that institute in step 3 Substrate is stated for transparent conducting glass.
8. a kind of preparation method of compound electrochromic membrane according to claim 7, it is characterised in that described transparent to lead Electric glass is ITO electro-conductive glass, AZO electro-conductive glass or FTO electro-conductive glass.
9. a kind of preparation method of compound electrochromic membrane according to claim 1, it is characterised in that institute in step 3 Substrate is stated for the porous substrate with metal film.
10. a kind of preparation method of compound electrochromic membrane according to claim 9, it is characterised in that the metal Film is golden film, silverskin or aluminium film.
CN201710355014.9A 2017-05-19 2017-05-19 A kind of preparation method of compound electrochromic membrane Active CN107032637B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710355014.9A CN107032637B (en) 2017-05-19 2017-05-19 A kind of preparation method of compound electrochromic membrane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710355014.9A CN107032637B (en) 2017-05-19 2017-05-19 A kind of preparation method of compound electrochromic membrane

Publications (2)

Publication Number Publication Date
CN107032637A true CN107032637A (en) 2017-08-11
CN107032637B CN107032637B (en) 2018-03-20

Family

ID=59538917

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710355014.9A Active CN107032637B (en) 2017-05-19 2017-05-19 A kind of preparation method of compound electrochromic membrane

Country Status (1)

Country Link
CN (1) CN107032637B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107382092A (en) * 2017-08-17 2017-11-24 浙江大学 TiO with Nanoparticles Embedded structure2 /WO3Compound electrochromic membrane and preparation method thereof
CN107512853A (en) * 2017-08-17 2017-12-26 浙江大学 Al with mosaic texture2O3/WO3Nano-composite electrochromic film and preparation method thereof
CN107512854A (en) * 2017-08-17 2017-12-26 浙江大学 ITO/WO with Nanoparticles Embedded structure3Compound electrochromic membrane and preparation method thereof
CN108732843A (en) * 2018-05-21 2018-11-02 上海交通大学 A kind of preparation method of electricity regulation and control chameleon bionic intelligence optically variable films
CN108761948A (en) * 2018-05-18 2018-11-06 清华大学 A kind of electrochromism method based on electrolyte
CN109188819A (en) * 2018-08-28 2019-01-11 上海幂方电子科技有限公司 A kind of flexible electro-chromic device and preparation method thereof
CN112552896A (en) * 2019-09-25 2021-03-26 四川大学 Electrochromic conductive polymer composite film and device preparation method
CN114563895A (en) * 2022-03-10 2022-05-31 四川大学 Porous conductive polymer-based electrochromic film and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101445617A (en) * 2009-01-06 2009-06-03 武汉工程大学 A preparation method of self-supporting polyaniline porous membrane
CN102153293A (en) * 2010-12-24 2011-08-17 南京工业大学 Preparation method for polyaniline and polyacrylic acid composite electrochromic film
WO2015162316A1 (en) * 2014-04-20 2015-10-29 Camarero Cerdán Ríchard Decontaminating and electrochromic polymer coating film
CN105236766A (en) * 2015-09-14 2016-01-13 西安科技大学 Method for preparing polyaniline electrochromic film through hydrothermal self-assembly
CN105951145A (en) * 2016-06-27 2016-09-21 河南师范大学 methylene blue doped polypyrrole electrochromism composite thin film and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101445617A (en) * 2009-01-06 2009-06-03 武汉工程大学 A preparation method of self-supporting polyaniline porous membrane
CN102153293A (en) * 2010-12-24 2011-08-17 南京工业大学 Preparation method for polyaniline and polyacrylic acid composite electrochromic film
WO2015162316A1 (en) * 2014-04-20 2015-10-29 Camarero Cerdán Ríchard Decontaminating and electrochromic polymer coating film
CN105236766A (en) * 2015-09-14 2016-01-13 西安科技大学 Method for preparing polyaniline electrochromic film through hydrothermal self-assembly
CN105951145A (en) * 2016-06-27 2016-09-21 河南师范大学 methylene blue doped polypyrrole electrochromism composite thin film and preparation method thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107382092A (en) * 2017-08-17 2017-11-24 浙江大学 TiO with Nanoparticles Embedded structure2 /WO3Compound electrochromic membrane and preparation method thereof
CN107512853A (en) * 2017-08-17 2017-12-26 浙江大学 Al with mosaic texture2O3/WO3Nano-composite electrochromic film and preparation method thereof
CN107512854A (en) * 2017-08-17 2017-12-26 浙江大学 ITO/WO with Nanoparticles Embedded structure3Compound electrochromic membrane and preparation method thereof
CN107512854B (en) * 2017-08-17 2020-05-08 浙江大学 ITO/WO with nano mosaic structure3Composite electrochromic film and preparation method thereof
CN107512853B (en) * 2017-08-17 2020-07-24 浙江大学 Al with mosaic structure 2O3/WO3Nano composite electrochromic film and preparation method thereof
CN108761948A (en) * 2018-05-18 2018-11-06 清华大学 A kind of electrochromism method based on electrolyte
CN108732843A (en) * 2018-05-21 2018-11-02 上海交通大学 A kind of preparation method of electricity regulation and control chameleon bionic intelligence optically variable films
CN108732843B (en) * 2018-05-21 2021-06-18 上海交通大学 Preparation method of electrically-controlled chameleon bionic intelligent color-changing film
CN109188819A (en) * 2018-08-28 2019-01-11 上海幂方电子科技有限公司 A kind of flexible electro-chromic device and preparation method thereof
CN112552896A (en) * 2019-09-25 2021-03-26 四川大学 Electrochromic conductive polymer composite film and device preparation method
CN114563895A (en) * 2022-03-10 2022-05-31 四川大学 Porous conductive polymer-based electrochromic film and preparation method thereof

Also Published As

Publication number Publication date
CN107032637B (en) 2018-03-20

Similar Documents

Publication Publication Date Title
CN107032637B (en) A kind of preparation method of compound electrochromic membrane
Shi et al. Broadly absorbing black to transmissive switching electrochromic polymers
Somani et al. Electrochromic materials and devices: present and future
Zeng et al. Colorless-to-black electrochromic devices based on ambipolar electrochromic system consisting of cross-linked poly (4-vinyltriphenylamine) and tungsten trioxide with high optical contrast in visible and near-infrared regions
US6667825B2 (en) Stable conjugated polymer electrochromic devices incorporating ionic liquids
CN106543415B (en) Thin polymer film and the preparation method and application thereof based on intersection construction conjugated molecule
CN110095913B (en) Preparation method of flexible self-supporting electrochromic film
CN114907551B (en) Red electrochromic polymer, preparation method, film and device
CN108957895A (en) Acid-base response electrochomeric films, preparation method and application and electrochromic device
KR101914393B1 (en) High performance electrochromic chromophores, application to electrochromic devices, and their operation method
CN113025304A (en) Electrochromic material and preparation method and application thereof
US20160109776A1 (en) Metal Sensitized Color Changing Material
CN112430314B (en) Electrochromic polymer containing indacenodithiophene structure, preparation method, polymer film and application
EP4083699A1 (en) Electrochromic device and electrochromic method therefor
Kanazawa et al. Electrochromic terpyridine-triphenylamine polymer films with high coloration efficiency in aqueous electrolyte
CN110501852A (en) A kind of electrochromic device and preparation method thereof based on highly concentrated water system electrolyte
Huang et al. Spectroelectrochemical and adhesion properties of chemically synthesized ion conducting poly (vinyl butyral) in Prussian blue and poly (3, 4-ethylenedioxythiophene) laminated electrochromic glazing
TWI609953B (en) Electrochromic composition and electrochromic element
CN106748868B (en) Organic compound, light modulation composition, and light modulation device
KR100508687B1 (en) Preparation of nanoelectrochromic films and electrochromic devices therefrom
CN105951145A (en) methylene blue doped polypyrrole electrochromism composite thin film and preparation method thereof
Yano et al. Multicolor expressible ECD materials consisted of polyaniline and anionic quinone
TW201248285A (en) Electrochromic device and method of manufacturing the same
CN115521442B (en) Solution-processable red-to-transparent electrochromic polymer and preparation method and application thereof
CN115417976B (en) Hydrophilic red to transparent electrochromic polymer and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant