CN115490836B - Electrochromic polymer capable of reversibly converting from yellow to high transmittance and application thereof - Google Patents
Electrochromic polymer capable of reversibly converting from yellow to high transmittance and application thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 238000002834 transmittance Methods 0.000 title description 4
- 229920006254 polymer film Polymers 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- JIMXXGFJRDUSRO-UHFFFAOYSA-N adamantane-1-carboxylic acid Chemical compound C1C(C2)CC3CC2CC1(C(=O)O)C3 JIMXXGFJRDUSRO-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- LNAMMBFJMYMQTO-FNEBRGMMSA-N chloroform;(1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical class [Pd].[Pd].ClC(Cl)Cl.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 LNAMMBFJMYMQTO-FNEBRGMMSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- HHXBZEIOUIMZET-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylphosphane Chemical compound ClC1=CC=CC(PC=2C=CC=CC=2)=C1Cl HHXBZEIOUIMZET-UHFFFAOYSA-N 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 13
- 230000002441 reversible effect Effects 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- NQRLWRODNCDUHY-UHFFFAOYSA-N 6-n,6-n,2-trimethylacridine-3,6-diamine Chemical compound C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3C=C21 NQRLWRODNCDUHY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006254 arylation reaction Methods 0.000 abstract 1
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 20
- 239000010408 film Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- -1 spin Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08G2261/10—Definition of the polymer structure
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Abstract
The invention discloses a soluble electrochromic polymer capable of realizing reversible conversion from yellow to high transmission and an electrochromic polymer film thereof. The invention adopts arylation polycondensation to prepare the electrochromic polymer. The invention also provides an electrochromic polymer film prepared from the electrochromic polymer, which can realize stable and reversible conversion from neutral yellow to oxidation state high transmission and has potential application value in the fields of displays, intelligent windows, mobile phone shells and the like.
Description
Technical Field
The invention relates to an electrochromic polymer with reversible transition from yellow to high transmission, a preparation method thereof and application thereof in preparing electrochromic polymer films.
Background
"Electrochromic" (Electrochromism, EC) refers to the phenomenon that optical properties of materials, such as transmittance, reflectance, absorptivity, etc., change steadily and reversibly under the action of an applied electric field, and macroscopically show reversible changes in color and transparency.
Electrochromic materials are mainly classified into inorganic electrochromic materials, organic small molecule electrochromic materials and polymer electrochromic materials. The polymer electrochromic material (PEC) has the characteristics of controllable energy band, good processing performance, excellent electrochromic comprehensive performance and the like because of the easy modification of the structure, and has great application value in the fields of intelligent windows, flat panel displays, information labels and the like, and is widely studied. PEC materials can be generally classified into electrochemically polymerized PEC materials and chemically polymerized PEC materials, depending on the manner of polymerization. Chemically polymerized PEC materials generally have good solution processability and thin films can be prepared by spray, spin, ink, screen, etc. techniques, thus allowing large area, low cost fabrication of PEC devices and, therefore, are of great interest.
In the last decade, solution processed PEC materials have been rapidly developed, and a wide variety of solution processed PEC materials have been designed for synthesis. Among them, soluble PEC materials with color to high transmission transition are widely studied, while CMY (cyan, magenta, and yellow) three primary colors to high transmission materials are important subjects of study, mainly because the three primary colors to high transmission materials are key to achieving full color regulation. However, currently three primary colors to high transmission materials are very few and electrochromic properties are poor. Furthermore, the design and synthesis of yellow to high-transmission materials are difficult, and the technical patents of yellow to high-transmission materials with good application prospects are concentrated in developed countries such as Europe and America, and the technical patents with independent intellectual property rights in the field are relatively lacking in China. Therefore, development of a novel yellow to high transmission solution processable PEC material with high performance and industrial application prospect is necessary.
Disclosure of Invention
A first object of the present invention is to provide an electrochromic polymer which can realize stable and reversible transition from neutral yellow to oxidized state with high transmission under the action of an electric field and has good solubility in organic solvents.
It is a second object of the present invention to provide a method for preparing electrochromic polymers.
A third object of the present invention is to provide an electrochromic polymer film.
The aim of the invention is achieved by the following technical scheme:
in a first aspect, the present invention provides an electrochromic polymer of formula (I),
Wherein: r is C 4～C30 alkyl;
The number average molecular weight Mn=2000-200000 of the electrochromic polymer, the molecular weight is controlled by polymerization time, and the polydispersity D=1.0-5.0.
Preferably, the electrochromic polymer has a number average molecular weight mn=5000 to 50000.
Preferably, R is C 6-C20 alkyl. More preferred is a C 8 alkyl group, especially 2-ethylhexyl.
In a second aspect, the present invention provides a method for preparing an electrochromic polymer represented by formula (I), which is prepared by arylating and polycondensing monomer 1 and monomer 2;
In formula 1, R is as defined in formula (I).
The preparation method of the polymer shown in the formula (I) specifically comprises the following steps: adding a monomer 1, a monomer 2, an organic acid, an inorganic weak base and a palladium catalyst into an organic solvent for polymerization reaction at 80-160 ℃ for 6-72 hours, and performing post-treatment on the obtained reaction liquid to obtain an electrochromic polymer shown in a formula (I); the ratio of the amounts of the substances of the monomer 1, the monomer 2, the organic acid, the inorganic weak base and the palladium catalyst is 1:1:0.3-0.5:2-3:0.03-0.1 (preferably 1:1:0.3:2.5:0.03).
Monomer 1 reference (adv. Mater.2010,22, 4949-4953) was synthesized using alcohols of different lengths to synthesize monomer 1 of different carbon chain lengths by condensation with alkyl bromides.
Preferably, the organic acid is one or a mixture of pivalic acid and 1-adamantanecarboxylic acid (preferably pivalic acid).
Preferably, the inorganic weak base is one or a mixture of more than two of potassium carbonate, sodium carbonate, cesium carbonate, potassium bicarbonate and sodium bicarbonate (preferably potassium carbonate).
Preferably, the palladium catalyst is one or a mixture of more than two of palladium acetate, dichloro-bis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium (0) -chloroform adducts (preferably palladium acetate).
Preferably, the organic solvent is one or a mixture of more than two of tetrahydrofuran, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide (preferably N, N-dimethylacetamide).
Preferably, the reaction temperature of the polymerization reaction is 120 to 140 ℃.
Preferably, the reaction time of the polymerization reaction is 12 to 36 hours.
Further, the volume of the organic solvent is 1 to 20L/mol (preferably 5L/mol) based on the total amount of the substances of the monomer 1 and the monomer 2 represented by the formula (I).
Further, the post-treatment is as follows: pouring the reaction solution into methanol, filtering, taking a filter cake, drying, sequentially extracting with methanol, acetone, hexane and chloroform by Soxhlet extraction, collecting a polymer dissolved in the chloroform, and spin-drying to obtain the electrochromic polymer shown in the formula (I).
In a third aspect, the present invention provides the use of an electrochromic polymer as described above in the preparation of an electrochromic polymer film.
Preferably, the electrochromic polymer film is obtained by processing the electrochromic polymer into a film through a solution.
Specifically, the application is: dissolving the electrochromic polymer in a solvent to obtain a polymer solution, and then coating the polymer solution on a conductive substrate to obtain the electrochromic polymer film; the solvent is one or more than two of dichloromethane, chloroform, tetrahydrofuran, toluene and N, N-dimethylformamide; the concentration of electrochromic polymer in the polymer solution is 5-30 mg/mL (preferably 15 mg/mL).
In the present invention, the coating may be spray coating, spin coating, screen printing, or the like. The conductive substrate can be ITO glass, FTO glass, an ITO-PET substrate, an FTO-PET substrate or the like.
The electrochromic polymer film obtained by the invention has potential application value in the fields of intelligent windows, displays, electronic papers and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polymer has good solubility in common organic solvents, and can realize large-area preparation of film materials by a solution processing method.
(2) The polymer film prepared by the invention can realize stable and reversible conversion from neutral yellow to high transmission in oxidation state, and has potential application value in the fields of displays, intelligent windows, mobile phone shells and the like.
Drawings
Fig. 1: the polymer film prepared in example 1 has optical absorption at different voltages;
Fig. 2: the polymer film prepared in example 1 has a time-dependent transmission profile at a specific wavelength from 0 to 1.3V multi-potential step.
Detailed Description
The technical scheme of the present invention is further described in the following specific examples, but the scope of the present invention is not limited thereto.
Example 1
The synthesis and molecular structure of the conjugated polymer used are as follows:
The synthesis process of the polymer is as follows:
M1 (0.44 g,1 eq.) and M2 (0.28 g,1 eq.) were added to a 10mLDMAc solution containing pivalic acid (30 mg,0.3 eq.) and potassium carbonate (345 mg,2.5 eq.) and finally Pd (OAc) 2 (7 mg,0.03 eq.) catalyst was added and reacted at 130℃for 24 hours. After the reaction is finished, the solution is poured into 200mL of methanol, filtered, a filter cake is taken and dried, methanol, acetone, hexane and chloroform are used for carrying out rope extraction in sequence, and polymers dissolved in the chloroform are collected and dried in a spinning way. Polymer GPC test results (mn=18.0 kda, d=2.76).
Preparation of a polymer film:
And (3) dissolving the polymer in chloroform to obtain a polymer solution, and spin-coating a film on an ITO substrate, wherein the concentration of the solution is 15mg/mL, the rotating speed is 800r/min, and the time is 1min. The volume of the solution obtained by spin coating was 0.5mL.
Electrochromic properties test of the resulting polymer films: the polymer films were colorimetrically tested in the 0V neutral state and in the 1.3V oxidation state, resulting in the neutral state l=91.98, a=0.13, b=82.8, oxidation state l=78.10, a=3.84, b=10.32. The prepared films were tested for uv-vis absorption at different voltages, transmittance at specific wavelengths and time, respectively, in 0.1M tetrabutylammonium hexafluorophosphate/acetonitrile solution using an electrochemical workstation and uv-vis spectrophotometer combination device, and the data processing results are shown in fig. 1 and 2. From FIG. 1 and the colorimetric test, it can be seen that the polymer film is yellow in a neutral state of 0V and is in a high transmission state after oxidation at a voltage of 1.3V. From FIG. 2, it can be seen that the contrast of the film at 446nm is 57.3%. Meanwhile, the coloring time and the fading time of the polymer film were 1.9s and 0.4s, respectively. A series of tests such as electrochemistry, ultraviolet-visible spectrophotometry, colorimeter and the like show that the prepared soluble electrochromic conjugated polymer can realize reversible conversion from yellow to high transmission and has excellent electrochromic comprehensive performance.
Claims (10)
1. An electrochromic polymer of formula (I),
Wherein: r is C 4～C30 alkyl;
The electrochromic polymer has a number average molecular weight mn=2000 to 200000.
2. A process for the preparation of electrochromic polymers of formula (I) according to claim 1, characterized in that it comprises:
adding a monomer 1, a monomer 2, an organic acid, an inorganic weak base and a palladium catalyst into an organic solvent for polymerization reaction at 80-160 ℃ for 6-72 hours, and performing post-treatment on the obtained reaction liquid to obtain an electrochromic polymer shown in a formula (I); the mass ratio of the monomer 1, the monomer 2, the organic acid, the inorganic weak base and the palladium catalyst is 1:1:0.3-0.5:2-3:0.03-0.1;
in the formula 1 and (I), R is C 4～C30 alkyl.
3. A process for the preparation of electrochromic polymers of formula (I) according to claim 2, characterized in that: the organic acid is one or a mixture of two of pivalic acid and 1-adamantanecarboxylic acid.
4. A process for the preparation of electrochromic polymers of formula (I) according to claim 2, characterized in that: the inorganic weak base is one or more than two of potassium carbonate, sodium carbonate, cesium carbonate, potassium bicarbonate and sodium bicarbonate.
5. A process for the preparation of electrochromic polymers of formula (I) according to claim 2, characterized in that: the palladium catalyst is one or a mixture of more than two of palladium acetate, dichloro-diphenyl phosphine palladium and tris (dibenzylideneacetone) dipalladium (0) -chloroform adducts.
6. A process for the preparation of electrochromic polymers of formula (I) according to claim 2, characterized in that: the organic solvent is one or more than two of tetrahydrofuran, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
7. A process for the preparation of electrochromic polymers of formula (I) according to claim 2, characterized in that: the volume of the organic solvent is 1-20L/mol based on the total mass of the monomer 1 and the monomer 2 shown in the formula (I).
8. A process for the preparation of electrochromic polymers of formula (I) according to claim 2, characterized in that the post-treatment is: pouring the reaction solution into methanol, filtering, taking a filter cake, drying, sequentially extracting with methanol, acetone, hexane and chloroform by Soxhlet extraction, collecting a polymer dissolved in the chloroform, and spin-drying to obtain the electrochromic polymer shown in the formula (I).
9. Use of an electrochromic polymer according to claim 1 for the preparation of an electrochromic polymer film.
10. The application according to claim 9, characterized in that the application is: dissolving the electrochromic polymer in a solvent to obtain a polymer solution, and then coating the polymer solution on a conductive substrate to obtain the electrochromic polymer film; the solvent is one or more than two of dichloromethane, chloroform, tetrahydrofuran, toluene and N, N-dimethylformamide; the concentration of electrochromic polymer in the polymer solution is 5-30 mg/mL.
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