CN104973805B - Conducting polymer Graphene compound electrochromic membrane and preparation method thereof - Google Patents
Conducting polymer Graphene compound electrochromic membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of conducting polymer Graphene compound electrochromic membrane, its preparation method is：First, one layer of conducting polymer thin film is deposited in conductive substrates by electrochemical polymerization method；Then, the Hummers methods by modifying prepare graphene oxide water solution, and are prepared for graphene film with stage reduction method by Metal Substrate self assembly；Finally, graphene film is covered in conducting polymer thin film surface by lifting transfer method, obtains compound electrochromic membrane；Compound electrochromic membrane structure of the present invention is novel, excellent performance, and preparation method is simple.
Description
(1) technical field
The present invention relates to compound electrochromic membrane and preparation method thereof, and in particular to a kind of conducting polymer-Graphene
Compound electrochromic membrane and preparation method thereof, the film has in fields such as smart window, display, Electronic Paper, capacitors
Extensive potential application.
(2) background technology
Electrochromism phenomenon refers under DC Electric Field, due to redox reaction or electric charge (electronics or ion)
Injection or extraction, the optical property (including transmissivity, absorptivity and reflectivity etc.) of material is in visible wavelength model
Interior generation inverible transform is enclosed, its macro manifestations possesses reversible transformation for the color of material with DC Electric Field.1961,
Platt for the first time propose electrochromism concept, 1969, Deb find first WO 3 film voltage effect under, its color
Mutual phase in version can occur and blueness between colourless, still later Sweden scientist C.G.Granqvist and American scientist
C.M.Lampert etc. proposes the thought for being used for novel energy saving window based on this electrochomeric films, and this causes electroluminescent change
Color thin-film material and device are prepared and turn into study hotspot.Electrochromic material is broadly divided into three major types from structure composition：It is inorganic
Electrochromic material (such as WO3), organic electrochromic material (such as purple sieve essence, polythiophene), composite electrochromic material (if any
Machine-inorganic hybridization).Wherein inorganic electrochromic material, color is single, and response speed is slow, but good stability；Organic Electricity mutagens
Color material, various colors, response speed is very fast, but less stable；And composite electrochromic material is in inorganic, organic electroluminescence
On the Research foundation of off-color material, the advantage and disadvantage of the two are scientifically and rationally cooperateed with, maximize its performance, this is also real
One main path of existing electrochromic material industrialization.
In the last few years, the discovery of continuing to develop with novel inorganic nano material, and new carbon such as C60, carbon receives
Mitron, Graphene etc., organic-inorganic nanocomposite electrochromic material becomes study hotspot, and wherein grapheme material grinds
Study carefully the most extensive.It is a kind of by the former molecular two-dimensional nano crystalline materials of individual layer C that graphite is dilute, both with big pi-conjugated organic
Condensed cyclic structure, imparts its excellent carrier conductivity, has the spies such as nano material specific surface area is big, chemical stability is good concurrently again
Point, therefore Graphene is incorporated into conducting polymer electrochromism (PEC) system, it is expected to improve interfacial interaction and electronics
Transmission performance, so as to obtain the more excellent electrochromic material of combination property.Stone congruent people high
(Polymer52.2011.5567-5572) to be prepared for graphene oxide-polyaniline (PIAN) multilayer by solution self-assembly method multiple
Electrochomeric films are closed, the electrochromism cyclical stability of the film makes moderate progress, but response time and contrast do not have
Change, be on the one hand probably that on the other hand the poorly conductive of electrode is probably because it is directly deposited on quartz glass plate
Because the composite membrane that this solution self assembly is obtained is of low quality.Gao Yan et al. (Adv.Mater.2011.23.1903-1908)
One layer of graphene oxide film is deposited on conjugated polymer P3HT surfaces, and this layer of composite membrane is used for organic solar batteries
In, the composite membrane using this surface of graphene oxide doping conjugated polymer is found as electric layer, not only the photoelectricity of battery turns
Efficiency is changed to increase, and the life-span of battery also extends well.Cao Xuebo et al. (Adv.Mater.2013.25.2957-
2962) graphene oxide is adsorbed in any transparency electrode using czochralski method, obtained film transmission rate is up to 89%；It is logical
Further electronation is crossed, large-sized high transmittance conductive graphene membrane is prepared.The preparation method not only solves stone
The problem that black alkene is easily reunited, so as to improve the transmission performance of electronics；The interface of graphene film and ITO electrode is enhanced simultaneously
Adhesion.
(3) content of the invention
It is an object of the invention to provide a kind of structure novelty, the exsertile conducting polymer of property-Graphene compound electric mutagens
Color film and preparation method thereof, involved Graphene is redox graphene in the present invention.
Technological process of the invention is：Electrochemical polymerization method prepares conducting polymer thin film (PEC) --- and tinsel is certainly
Assembling syn-depositional reducing process prepares graphene film (CCG) --- and lifting transfer method prepares conducting polymer-Graphene and is combined
Electrochomeric films (PEC-CCG).
The present invention is adopted the following technical scheme that：
A kind of conducting polymer-Graphene compound electrochromic membrane, described compound electrochromic membrane is by as follows
What method was prepared：
(1) preparation of conducting polymer thin film：Electroanalysis solvent, conducting polymer monomer and supporting electrolyte are added into three electricity
Electrolyte is configured in the electrolytic cell of pole, in gained electrolyte, the initial concentration of the conducting polymer monomer for 0.0005~
0.01mol/L, the concentration of the supporting electrolyte is 0.001~0.1mol/L；Described three-electrode cell is with conductive substrates
Ito glass electrode or flexibility ITO-PET electrodes are working electrode, are auxiliary electrode with gold or platinum electrode, with calomel electrode or silver-
Silver chloride electrode is reference electrode；The electrolyte uses potentiostatic method in three-electrode cell under the conditions of 1.2~1.5V
Carry out polymerisation, polymerization terminates when polymerization consumption electricity reaches 0.01~0.1C, be -0.4~-0.6V to poly- by control of Electric potentials
Closing reacted working electrode carries out dedoping 100~200s for the treatment of, and the working electrode after cleaning dedoping with electroanalysis solvent is put
Enter drying in vacuum drying chamber, obtain final product the conducting polymer thin film being deposited in conductive substrates；
Wherein, described electroanalysis solvent is one or both of acetonitrile, dichloromethane with the mixed liquor of arbitrary proportion；Institute
The conducting polymer monomer stated is selected from one of following：4,4', 4 "-three (two bithiophenes) triphenylamine, 1,4- bis- (3- thienyls) benzene,
3-4 ethene dioxythiophenes, thiophene, aniline；Described supporting electrolyte is tetrabutylammonium perchlorate, lithium perchlorate or tetrabutyl fluorine
Ammonium borate；
(2) preparation of graphene film：Concentrated sulfuric acid A, potassium peroxydisulfate, phosphorus pentoxide are sequentially added in graphite powder,
After reacting 6~8h at 75~85 DEG C, filtering, filter cake deionized water A is washed till neutrality, and drying obtains pre-oxidizing graphite；In gained
Concentrated sulfuric acid B, sodium nitrate are added in pre-oxidation graphite, potassium permanganate is slowly added at 0~5 DEG C, react 2 at 35~40 DEG C~
After 3h, 0~5 DEG C is cooled to, sequentially adds the H of deionized water B, 30wt%~40wt%2O2The aqueous solution is reacted so that reaction is quenched
Mixture obtains graphene oxide, gained graphene oxide is added in deionized water C through centrifugation, cleaning, and 3~6h of ultrasound is obtained
To graphene oxide water solution, gained graphene oxide water solution through dilution make the concentration of wherein graphene oxide for 0.1~
The graphene oxide water solution that 0.5mg/L is diluted, then tinsel is dipped into the graphene oxide water solution of the dilution
In, dip time was controlled at 15~30 minutes, then took out tinsel, was dried in atmosphere, and obtaining final product deposition has Graphene thin
The tinsel of film；
Wherein, the graphite powder and the mass ratio that feeds intake of potassium peroxydisulfate, phosphorus pentoxide are 1：2~3：2~3；It is described dense
The volumetric usage of sulfuric acid A is calculated as 10~14mL/g with the quality of graphite powder；The graphite powder and sodium nitrate, potassium permanganate feed intake
Mass ratio is 1：0.6~1：3~5；The volumetric usage of the concentrated sulfuric acid B is calculated as 32~36mL/g with the quality of graphite powder；It is described
The volumetric usage of deionized water B is calculated as 50~100mL/g, the H of the 30wt%~40wt% with the quality of graphite powder2O2It is water-soluble
The volumetric usage of liquid is calculated as 4~6mL/g with the quality of graphite powder；
(3) preparation of laminated film：The tinsel that the deposition that step (2) is obtained has graphene film is put into corrosive liquid
In, graphene film is obtained after eroding tinsel, graphene film is then covered in step (1) by lifting transfer method
The conducting polymer thin film surface being deposited in conductive substrates for obtaining, that is, obtain laminated film, and the graphene film
The conducting polymer thin film is completely covered, i.e., the area coverage of described graphene film is more than or equal to the conducting polymer
The area of film.
Conducting polymer of the present invention-Graphene compound electrochromic membrane, in step (1), described electroanalysis solvent is preferred
Acetonitrile and methylene chloride volume compare 1：3~5 mixed liquor.
In step (1), described conducting polymer monomer is usually thiophene-based, triphen amine, carbazole organic micromolecule,
It is preferred that thiophene-triphen amine derivant, specific preferably 4,4', 4 "-three (two bithiophenes) triphenylamines or Isosorbide-5-Nitrae-two (3- thienyls)
Benzene.
In step (1), described auxiliary electrode is preferably platinum electrode；Described reference electrode is preferably silver-silver chloride electricity
Pole.
In step (2), after the reactant mixture is through centrifugation, the method for the cleaning is：First use 4wt%~10wt%
HCl/water solution clean 3~5 times with remove residual metal ions, then cleaned with deionized water to neutrality obtain graphite oxide
Alkene.
In step (2), described tinsel is generally selected from copper sheet, nickel sheet or zinc metal sheet, preferably copper sheet, and preferably copper sheet
Thickness is 0.08~0.5mm.
In step (3), described corrosive liquid is generally selected from ferric chloride aqueous solutionses, iron nitrate aqueous solution, ammonium persulfate water
Solution or sodium thiosulfate solution, also, described ferric chloride aqueous solutionses, iron nitrate aqueous solution, ammonium persulfate aqueous solution
Or the concentration of sodium thiosulfate solution is 0.1~1mol/L.It is preferred that ferric chloride aqueous solutionses, and ferric trichloride preferably wherein
Concentration be 0.1~0.3mol/L.
In step (3), preferably described laminated film has bridge linking type structure, i.e., the area coverage of described graphene film is big
It is in the area of the conducting polymer thin film and multiple with conductive substrates beyond the two ends that part is located at conducting polymer thin film
Close, formed with conducting polymer thin film as bridge pier, the bridge linking type laminated film with graphene film as bridge.The present invention is by electricity
Chemical property is tested, it was confirmed that the response speed of this " bridge linking type " conducting polymer-Graphene compound electrochromic membrane has
Significantly improve.
Involved term in the present invention：" concentrated sulfuric acid A ", " concentrated sulfuric acid B ", without special implication, are referred both on ordinary meaning
The concentrated sulfuric acid, namely the concentrated sulfuric acid that mass fraction is 98% is only intended to distinguish institute in different operating step labeled as " A ", " B "
The concentrated sulfuric acid used, equally, " deionized water A ", " deionized water B ", " deionized water C " are also the deionization on ordinary meaning
Water, is also only intended to distinguish used deionized water in different operating step labeled as " A ", " B ", " C ".
Compared with prior art, the beneficial effect of heretofore described compound electrochromic membrane is mainly reflected in：
(1) " bridge linking type " composite construction, structure is novel, and performance is protruded；
(2) graphene film is prepared using Metal Substrate self assembly syn-depositional reducing process, simple to operate, film thickness can
Control, synchronous reduction, it is easy to shift, translucency is good.
(4) illustrate
Fig. 1 is present invention process schematic flow sheet；
Fig. 2 is " bridge linking type " conducting polymer-Graphene composite electrochromic resulting on ITO- glass in embodiment 1
Digital photographing figure in film under condition；
Fig. 3 is spectroelectrochemistry figure of the compound conducting polymer thin film of unused Graphene at 1100nm in embodiment 1；
Fig. 4 is " bridge linking type " conducting polymer-light of the Graphene compound electrochromic membrane at 1100nm in embodiment 1
Spectrum electrochemistry figure；
Fig. 5 is " bridge linking type " conducting polymer-Graphene composite electrochromic resulting on ITO- glass in embodiment 2
Digital photographing figure in film under condition；
Fig. 6 is spectroelectrochemistry figure of the compound conducting polymer thin film of unused Graphene at 1100nm in embodiment 2；
Fig. 7 is embodiment 2 " bridge linking type " conducting polymer-spectrum of the Graphene compound electrochromic membrane at 1100nm
Electrochemistry figure.
(5) specific embodiment
Technical scheme is further described with specific embodiment below, but protection scope of the present invention is not
It is limited to this.
Embodiment 1
Conducting polymer monomer is 4,4', 4 "-three (two bithiophenes) triphenylamines (TBTPA)
(1) conducting polymer thin film is prepared：By the mixed liquor (volume ratio 3 of electroanalysis solvent acetonitrile and dichloromethane:7)
50ml, monomer (0.0276g, 0.75mM) and supporting electrolyte tetrabutylammonium perchlorate (TBAP, 1.71g, 0.1M) uniformly mix
Be configured to electrolyte, be then added in three-electrode cell, wherein working electrode be ito glass electrode (its size be 0.9 ×
4cm), auxiliary electrode is platinum electrode, and reference electrode is silver-silver chloride electrode.Gathered using potentiostatic method under the conditions of 1.2V
Reaction is closed, when polymerization consumption electricity reaches 0.06C, polymerization terminates, and working electrode ITO conductive glass surfaces deposited blue layer
Polymer film, by control of Electric potentials be -0.6V when, the working electrode after polymerisation is carried out dedoping treatment 100s, find
Color is changed into orange-yellow, then to be cleaned after dedoping with electrolysis solvent acetonitrile and dichloromethane mixed liquor work electricity by blueness
Pole, is put into vacuum drying chamber and dries stand-by, "-three (two bithiophenes) triphens that obtain being deposited on the polymerization 4,4', 4 on ito glass
Amine film (PTBTPA), its spectroelectrochemistry figure at 1100nm is shown in Fig. 3.
(2) graphene film is prepared：By the concentrated sulfuric acid (12ml), potassium peroxydisulfate (2.5g), phosphorus pentoxide (2.5g) successively
It is added in graphite powder (1g), 6h is reacted at 80 DEG C, after reaction terminates, filtering, filter cake is washed with deionized water to neutrality, drying
Obtain pre-oxidizing graphite, the concentrated sulfuric acid (34ml), sodium nitrate (0.75g) are added in product is pre-oxidized, be slowly added at 0 DEG C
Potassium permanganate (5g), reacts 2h at 40 DEG C, after reaction terminates, be cooled to 0 DEG C, sequentially adds 100ml deionized waters, 4ml H2O2
(30wt%) aqueous solution is quenched reaction, and then reactant mixture centrifugation first uses 4wt%HCl aqueous cleanings (100mL × 4 time)
With remove residual metal ion, then cleaned with deionized water to neutrality obtain graphene oxide, by gained graphene oxide
It is added in deionized water, ultrasonic 5h obtains graphene oxide water solution, gained graphene oxide water solution makes wherein oxygen through dilution
The concentration of graphite alkene is 0.1mg/L, then the clean smooth metal copper sheet in surface is invaded into graphene oxide water solution
In (0.1mg/L), dip time 30 minutes is then careful to take out metal copper sheet, dries in atmosphere, heavy on metal copper sheet surface
One layer of graphene film of brownish black (CCG) is accumulated.
(3) laminated film is prepared：The metal copper sheet that will deposit has CCG is put into and is carefully placed on FeCl3The aqueous solution (0.1mol/
L) surface, after Copper Foil corrodes completely, then CCG will be covered in deposition by CCG exposed to solution surface by lifting transfer method
Have an ITO- glass surfaces of PTBTPA, and CCG coverings PTBTPA the two ends that PTBTPA is located at beyond part, formed with
PTBTPA is bridge pier, the bridge linking type PTBTPA-CCG compound electrochromic membranes with CCG as bridge, its spectrum at 1100nm
Electrochemistry figure is shown in Fig. 4.
Embodiment 2
Monomer changes 1,4- bis- (3- thienyls) benzene (DTB) into
(1) conducting polymer thin film is prepared：By electroanalysis solvent dichloromethane 50ml, monomer (0.0242g, 2mM) and support
Electrolyte tetrabutylammonium perchlorate (TBAP, 1.71g, 0.1M) is uniformly hybridly prepared into electrolyte, is then added to three electrodes electricity
Xie Chizhong, wherein working electrode are ito glass (its size be 0.9 × 4cm), and auxiliary electrode is platinum electrode, reference electrode for silver-
Silver chloride electrode.Polymerisation is carried out using potentiostatic method under the conditions of polymerization current potential 1.3V, polymerization consumption electricity reaches 0.04C
When, polymerization terminates, and working electrode ito glass electrode surface deposited one layer of polymer film of yellow, is -0.6V by control of Electric potentials
When, dedoping treatment 100s is carried out to the working electrode after polymerisation, it is found that color is changed into blueness by yellow, then electricity consumption
Working electrode after solution methylene chloride cleaning dedoping, is put into vacuum drying chamber and dries stand-by, obtains being deposited on ITO glass
Polymerization Isosorbide-5-Nitrae-two (3- thienyls) benzene film (PDTB) on glass, its spectroelectrochemistry figure at 1100nm is shown in Fig. 6.
(2) graphene film is prepared：By the concentrated sulfuric acid (12ml), potassium peroxydisulfate (2.5g), phosphorus pentoxide (2.5g) successively
It is added in graphite powder (1g), 6h is reacted at 80 DEG C, after reaction terminates, filtering, filter cake is washed with deionized water to neutrality, drying
Obtain pre-oxidizing graphite, the concentrated sulfuric acid (34ml), sodium nitrate (0.75g) are added in graphite is pre-oxidized, be slowly added at 0 DEG C
Potassium permanganate (5g), reacts 2h at 40 DEG C, after reaction terminates, be cooled to 0 DEG C, sequentially adds 100ml deionized waters, 4ml H2O2
(30wt%) aqueous solution is quenched reaction, and then reactant mixture centrifugation first uses 4wt%HCl aqueous cleanings (100mL × 4 time)
With remove residual metal ion, then cleaned with deionized water to neutrality obtain graphene oxide, by gained graphene oxide
It is added in deionized water, ultrasonic 5h obtains graphene oxide water solution, gained graphene oxide water solution makes wherein oxygen through dilution
The concentration of graphite alkene is 0.1mg/L, then the clean smooth metal copper sheet in surface is invaded into graphene oxide water solution
In (0.1mg/L), dip time 30 minutes is then careful to take out metal copper sheet, dries in atmosphere, heavy on metal copper sheet surface
One layer of graphene film of brownish black (CCG) is accumulated.
(3) laminated film is prepared：The metal copper sheet that will deposit has CCG is put into and is carefully placed on FeCl3The aqueous solution (0.1mol/
L) surface, after Copper Foil corrodes completely, then CCG will be covered in deposition by CCG exposed to solution surface by lifting transfer method
There are the ITO- glass surfaces of PDTB, and CCG covers the two ends that PDTB is located at beyond part of PDTB, is formed with PDTB as bridge
Pier, the bridge linking type PDTB-CCG compound electrochromic membranes with CCG as bridge, its spectroelectrochemistry figure at 1100nm is shown in figure
7。
The film and pure conducting polymer thin film after being combined are can be seen that by the data of Fig. 3 and Fig. 4, Fig. 6 and Fig. 7
Response speed is significantly improved.In embodiment 1, the fading time and coloration time of pure conducting polymer thin film are respectively：
1.6s and 4.3s, and the fading time and coloration time of " bridge linking type " the structure composite film being combined with Graphene are respectively：
1.0s and 3.5s；In embodiment 2, the fading time and coloration time of pure conducting polymer thin film are respectively 1.0s and 4.5s,
And the fading time and coloration time of " bridge linking type " the structure composite film being combined with Graphene are respectively：0.6s and 3.4s, phase
Than in existing some conducting polymers and the compound electrochromic material of Graphene, the amplitude that the complex method is improved is bigger.
Claims (10)
1. a kind of conducting polymer-Graphene compound electrochromic membrane, it is characterised in that described compound electrochromic membrane
It is prepared as follows what is obtained：
(1) preparation of conducting polymer thin film：Electroanalysis solvent, conducting polymer monomer and supporting electrolyte are added into three electrodes electricity
Xie Chizhong is configured to electrolyte, in gained electrolyte, the initial concentration of the conducting polymer monomer for 0.0005~
0.01mol/L, the concentration of the supporting electrolyte is 0.001~0.1mol/L；Described three-electrode cell is with conductive substrates
Ito glass electrode or flexibility ITO-PET electrodes are working electrode, are auxiliary electrode with gold or platinum electrode, with calomel electrode or silver-
Silver chloride electrode is reference electrode；The electrolyte uses potentiostatic method in three-electrode cell under the conditions of 1.2~1.5V
Carry out polymerisation, polymerization terminates when polymerization consumption electricity reaches 0.01~0.1C, be -0.4~-0.6V to poly- by control of Electric potentials
Closing reacted working electrode carries out dedoping 100~200s for the treatment of, and the working electrode after cleaning dedoping with electroanalysis solvent is put
Enter drying in vacuum drying chamber, obtain final product the conducting polymer thin film being deposited in conductive substrates；
Wherein, described electroanalysis solvent is one or both of acetonitrile, dichloromethane with the mixed liquor of arbitrary proportion；Described
Conducting polymer monomer is selected from one of following：4,4', 4 "-three (two bithiophenes) triphenylamine, 1,4- bis- (3- thienyls) benzene, 3,4-
Ethene dioxythiophene, thiophene, aniline；Described supporting electrolyte is tetrabutylammonium perchlorate, lithium perchlorate or tetrabutyl fluorine boron
Sour ammonium；
(2) preparation of graphene film：Concentrated sulfuric acid A, potassium peroxydisulfate, phosphorus pentoxide are sequentially added in graphite powder, 75~
After reacting 6~8h at 85 DEG C, filtering, filter cake deionized water A is washed till neutrality, and drying obtains pre-oxidizing graphite；In the pre- oxygen of gained
Concentrated sulfuric acid B, sodium nitrate are added in graphite, potassium permanganate is slowly added at 0~5 DEG C, 2~3h is reacted at 35~40 DEG C
Afterwards, 0~5 DEG C is cooled to, the H of deionized water B, 30wt%~40wt% is sequentially added2O2The aqueous solution is to be quenched reaction, and reaction is mixed
Compound obtains graphene oxide, gained graphene oxide is added in deionized water C through centrifugation, cleaning, and 3~6h of ultrasound is obtained
Graphene oxide water solution, gained graphene oxide water solution through dilution make the concentration of wherein graphene oxide for 0.1~
The graphene oxide water solution that 0.5mg/L is diluted, then tinsel is dipped into the graphene oxide water solution of the dilution
In, dip time was controlled at 15~30 minutes, then took out tinsel, was dried in atmosphere, and obtaining final product deposition has Graphene thin
The tinsel of film；
Wherein, the graphite powder and the mass ratio that feeds intake of potassium peroxydisulfate, phosphorus pentoxide are 1：2~3：2~3；The concentrated sulfuric acid A
Volumetric usage 10~14mL/g is calculated as with the quality of graphite powder；The graphite powder and sodium nitrate, the quality that feeds intake of potassium permanganate
Than being 1：0.6~1：3~5；The volumetric usage of the concentrated sulfuric acid B is calculated as 32~36mL/g with the quality of graphite powder；It is described go from
The volumetric usage of sub- water B is calculated as 50~100mL/g, the H of the 30wt%~40wt% with the quality of graphite powder2O2The aqueous solution
Volumetric usage is calculated as 4~6mL/g with the quality of graphite powder；
(3) preparation of laminated film：The tinsel that the deposition that step (2) is obtained has graphene film is put into corrosive liquid,
Graphene film is obtained after eroding tinsel, graphene film is then covered in step (1) by lifting transfer method
To the conducting polymer thin film surface being deposited in conductive substrates, that is, obtain laminated film, and the graphene film is complete
Conducting polymer thin film described in all standing, i.e., the area coverage of described graphene film is thin more than or equal to the conducting polymer
The area of film.
2. compound electrochromic membrane as claimed in claim 1, it is characterised in that in step (1), described electroanalysis solvent is
Acetonitrile and methylene chloride volume compare 1：3~5 mixed liquor.
3. compound electrochromic membrane as claimed in claim 1, it is characterised in that in step (1), described conducting polymer
Monomer is 4,4', 4 "-three (two bithiophenes) triphenylamines or 1,4- bis- (3- thienyls) benzene.
4. compound electrochromic membrane as claimed in claim 1, it is characterised in that in step (2), the reactant mixture warp
After centrifugation, the method for the cleaning is：First with 3~5 metals to remove residual of 4wt%~10wt%HCl aqueous cleanings
Ion, then cleaned with deionized water to neutrality obtain graphene oxide.
5. compound electrochromic membrane as claimed in claim 1, it is characterised in that in step (2), described tinsel choosing
From copper sheet, nickel sheet or zinc metal sheet.
6. compound electrochromic membrane as claimed in claim 1, it is characterised in that in step (2), described tinsel is
Copper sheet, and the thickness of copper sheet is 0.08~0.5mm.
7. compound electrochromic membrane as claimed in claim 1, it is characterised in that in step (3), described corrosive liquid is selected from
Ferric chloride aqueous solutionses, iron nitrate aqueous solution, ammonium persulfate aqueous solution or sodium thiosulfate solution.
8. compound electrochromic membrane as claimed in claim 7, it is characterised in that described ferric chloride aqueous solutionses, nitric acid
The concentration of water solution, ammonium persulfate aqueous solution or sodium thiosulfate solution is 0.1~1mol/L.
9. compound electrochromic membrane as claimed in claim 1, it is characterised in that in step (3), described corrosive liquid is three
The concentration of ferric chloride in aqueous solution, wherein ferric trichloride is 0.1~0.3mol/L.
10. compound electrochromic membrane as claimed in claim 1, it is characterised in that in step (3), the laminated film tool
There are bridge linking type structure, i.e., the area of the area coverage more than the conducting polymer thin film of described graphene film, and exceed
Part is located at the two ends of conducting polymer thin film and conductive substrates are combined, and is formed with conducting polymer thin film as bridge pier, with graphite
Alkene film is the bridge linking type laminated film of bridge.
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| CN115236911A (en) * | 2022-07-11 | 2022-10-25 | 贵州大学 | Method for preparing electrochromic visible light infrared regulation and control intelligent material and material |
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