CN109593224B - Preparation method of flexible polyaniline/poly-o-toluidine double-layer electrochromic film - Google Patents

Preparation method of flexible polyaniline/poly-o-toluidine double-layer electrochromic film Download PDF

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CN109593224B
CN109593224B CN201811538739.2A CN201811538739A CN109593224B CN 109593224 B CN109593224 B CN 109593224B CN 201811538739 A CN201811538739 A CN 201811538739A CN 109593224 B CN109593224 B CN 109593224B
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李垚
张雷鹏
赵九蓬
王博
李晓白
徐高平
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Abstract

A preparation method of a flexible polyaniline/poly-o-toluidine double-layer electrochromic film relates to a preparation method of a double-layer electrochromic film. The invention aims to solve the problem that the existing intelligent material is poor in infrared emissivity regulation and control capability. The method comprises the following steps: firstly, preparing a poly-o-toluidine solution; secondly, preparing a poly-o-toluidine film; thirdly, preparing a polyaniline solution; and fourthly, preparing the polyaniline film to obtain the flexible polyaniline/poly-o-toluidine double-layer electrochromic film. The flexible aniline/poly-o-toluidine composite electrochromic film prepared by the invention has high infrared regulation and control capability and good cycle stability, and can meet the demand of the national defense field on photo-thermal intelligent regulation and control. The invention can obtain a flexible polyaniline/poly-o-toluidine double-layer electrochromic film.

Description

Preparation method of flexible polyaniline/poly-o-toluidine double-layer electrochromic film
Technical Field
The invention relates to a preparation method of a double-layer electrochromic film.
Background
Light and heat are the basis of human survival and development, and with the rapid development of fields such as renewable energy, communication, optics, mechanical manufacturing, aerospace technology, national defense and the like, higher requirements are put forward on the radiation characteristic and directivity of infrared light, and breakthrough of high-performance photo-thermal regulation materials and technologies is urgently needed, so that the intelligent regulation of mid-far infrared light is realized, and the high-performance photo-thermal regulation materials and technologies are applied to the military field to improve the national defense construction of China. Can realize the intelligent regulation to the infrared light through the stimulation of external photoelectricity heat at present, be called intelligent light and heat regulation and control technique, mainly divide into three kinds: photochromic photothermal regulation and control technology, electrochromic photothermal regulation and control technology and thermochromic photothermal regulation and control technology. The electrochromic photo-thermal regulation technology can realize active regulation, and meanwhile, the structural design of materials and devices can realize multi-spectral-band and multi-level intelligent regulation, and the electrochromic photo-thermal regulation technology is low in energy consumption and high in response speed and is widely concerned and researched.
The electrochromic photo-thermal regulation technology is a phenomenon that by applying alternating high-low or positive-negative external electric fields and injecting or extracting charges (ions or electrons), the valence state and components of a material are reversibly changed, and then the optical properties (transmittance, reflectivity and absorptivity) of the material in an infrared band are reversibly changed. Therefore, intelligent control of infrared radiation light can be realized by utilizing the characteristic. Compared with other photo-thermal regulation technologies, the electrochromic photo-thermal regulation technology is an active regulation technology, can be controlled in real time to realize the change of the optical properties of the material, is more suitable for the photo-thermal regulation of a complex environment, and can meet the demand of the national defense field on photo-thermal intelligent regulation. At present, electrochromic photo-thermal regulation materials which are researched more at home and abroad are mainly divided into organic electrochromic materials and inorganic electrochromic materials.
The published documents mainly surround single-component materials or mixed integrated composite materials to realize intelligent regulation and control of infrared radiation characteristics, but the infrared regulation and control capability is relatively limited, and the infrared emissivity is about 0.28.
Disclosure of Invention
The invention aims to solve the problem of poor infrared emissivity regulation and control capability of the existing intelligent material, and provides a preparation method of a flexible polyaniline/poly-o-toluidine double-layer electrochromic film.
A preparation method of a flexible polyaniline/poly-o-toluidine double-layer electrochromic film is completed according to the following steps:
firstly, preparing a poly-o-toluidine solution:
①, preparing an acid solution with the concentration of 0.1 mol/L-1 mol/L by taking deionized water as a solvent;
②, adding the distilled o-toluidine into the acid solution with the concentration of 0.1 mol/L-1 mol/L prepared in the step one ①, and magnetically stirring at the stirring speed of 200 r/min-400 r/min until the solution is clear to obtain an o-toluidine acid solution;
the mol ratio of the o-methylbenzylamine to the acid in the o-methylbenzylamine acid solution in the first step ② is 1 (2-10);
③, adding ammonium persulfate into the acid solution with the concentration of 0.1 mol/L-1 mol/L prepared in the step one ①, and magnetically stirring for 5-10 min at the stirring speed of 200-500 r/min to obtain an ammonium persulfate acid solution;
the molar ratio of ammonium persulfate to acid in the ammonium persulfate acid solution in the first step ③ is (1-1.5): 5;
④, adding an ammonium persulfate solution into an o-toluidine acid solution, reacting for 20-26 h at 0-5 ℃, and performing vacuum filtration to obtain a solid matter I, firstly, drying the solid matter I in vacuum for 20-24 h at 55-65 ℃, and then grinding to obtain acid-doped poly-o-toluidine powder;
the volume ratio of the ammonium persulfate solution to the o-toluidine acid solution in the first step ④ is (0.5-1): 1;
the mass fraction of the acid-doped poly-o-toluidine solution in the first step ④ is 1-20%;
secondly, preparing a poly-o-toluidine film:
spin-coating or spraying the acid-doped poly-o-toluidine solution on the surface of a substrate, and naturally drying to form an acid-doped poly-o-toluidine film on the surface of the substrate;
the substrate in the second step is an ITO flexible conductive film or a porous gold film;
thirdly, preparing a polyaniline solution:
①, adding distilled aniline into the acid solution with the concentration of 0.1 mol/L-1 mol/L prepared in the step one ①, and magnetically stirring at the stirring speed of 200 r/min-500 r/min until the solution is clear to obtain an aniline acid solution;
the molar ratio of aniline to acid in the aniline acid solution in the third ① is 1 (2-10);
②, adding the ammonium persulfate acid solution prepared in the first step ③ into an aniline acid solution, reacting for 20-26 h at the temperature of 0-5 ℃, and performing vacuum filtration to obtain a solid matter II, firstly, performing vacuum drying on the solid matter II for 20-24 h at the temperature of 55-65 ℃, then, grinding to obtain acid-doped polyaniline powder, and dissolving the acid-doped polyaniline powder into N, N-dimethylformamide to obtain an acid-doped polyaniline solution;
the volume ratio of the ammonium persulfate acid solution to the aniline acid solution in the third step ② is (0.5-1): 1;
the mass fraction of the acid-doped polyaniline solution in the step three ② is 1-20%;
fourthly, preparing the polyaniline film:
and (3) spin-coating or spraying the acid-doped polyaniline solution on the acid-doped poly-o-toluidine film obtained in the step two, naturally drying, and forming an acid-doped polyaniline film on the acid-doped poly-o-toluidine film to obtain the flexible polyaniline/poly-o-toluidine double-layer electrochromic film.
The principle and the advantages of the invention are as follows:
according to the invention, o-toluidine is used as a synthetic monomer of a functional material at the bottom layer of the flexible polyaniline/poly-o-toluidine composite electrochromic film, as a substituent is introduced on a benzene ring, side reaction at an ortho position can be effectively prevented, and a free radical polymerization reaction at the para position is promoted, so that a long-chain conjugated structure is obtained, and meanwhile, a methyl group which is provided with an electron-donating group and has small steric hindrance is introduced at the ortho position of the benzene ring, so that the prepared film is more compact, the conductivity of a substrate is further changed, and then a rough acid-doped polyaniline film is prepared on the basis, so that the construction of a double-layer composite structure is realized;
the flexible aniline/poly-o-toluidine composite electrochromic film prepared by the invention has high infrared regulation and control capability and good cycle stability, and can meet the demand of the national defense field on photo-thermal intelligent regulation and control;
and thirdly, the infrared emissivity of the flexible polyaniline/poly-o-toluidine double-layer electrochromic film prepared by the invention can reach 0.348.
The invention can obtain a flexible polyaniline/poly-o-toluidine double-layer electrochromic film.
Drawings
Fig. 1 is a schematic structural diagram of a flexible polyaniline/poly-o-toluidine double-layer electrochromic film according to a first embodiment, in which fig. 1 is a substrate, 2 is an acid-doped poly-o-toluidine film, and 3 is an acid-doped polyaniline film;
FIG. 2 is an SEM image of an acid-doped poly-o-toluidine thin film obtained in step two of the example;
FIG. 3 is an SEM image of a flexible polyaniline/poly-o-toluidine bilayer electrochromic film obtained in step four of the example;
fig. 4 is an infrared emissivity curve of the flexible polyaniline/poly-o-tolylamine double-layer electrochromic film obtained in step four of the embodiment, where 1 is-0.25V and 2 is 0.45V.
Detailed Description
The first embodiment is as follows: referring to fig. 1, the present embodiment is described, and the method for preparing a flexible polyaniline/poly-o-toluidine double-layer electrochromic film according to the present embodiment is completed according to the following steps:
firstly, preparing a poly-o-toluidine solution:
①, preparing an acid solution with the concentration of 0.1 mol/L-1 mol/L by taking deionized water as a solvent;
②, adding the distilled o-toluidine into the acid solution with the concentration of 0.1 mol/L-1 mol/L prepared in the step one ①, and magnetically stirring at the stirring speed of 200 r/min-400 r/min until the solution is clear to obtain an o-toluidine acid solution;
the mol ratio of the o-methylbenzylamine to the acid in the o-methylbenzylamine acid solution in the first step ② is 1 (2-10);
③, adding ammonium persulfate into the acid solution with the concentration of 0.1 mol/L-1 mol/L prepared in the step one ①, and magnetically stirring for 5-10 min at the stirring speed of 200-500 r/min to obtain an ammonium persulfate acid solution;
the molar ratio of ammonium persulfate to acid in the ammonium persulfate acid solution in the first step ③ is (1-1.5): 5;
④, adding an ammonium persulfate solution into an o-toluidine acid solution, reacting for 20-26 h at 0-5 ℃, and performing vacuum filtration to obtain a solid matter I, firstly, drying the solid matter I in vacuum for 20-24 h at 55-65 ℃, and then grinding to obtain acid-doped poly-o-toluidine powder;
the volume ratio of the ammonium persulfate solution to the o-toluidine acid solution in the first step ④ is (0.5-1): 1;
the mass fraction of the acid-doped poly-o-toluidine solution in the first step ④ is 1-20%;
secondly, preparing a poly-o-toluidine film:
spin-coating or spraying the acid-doped poly-o-toluidine solution on the surface of a substrate, and naturally drying to form an acid-doped poly-o-toluidine film on the surface of the substrate;
the substrate in the second step is an ITO flexible conductive film or a porous gold film;
thirdly, preparing a polyaniline solution:
①, adding distilled aniline into the acid solution with the concentration of 0.1 mol/L-1 mol/L prepared in the step one ①, and magnetically stirring at the stirring speed of 200 r/min-500 r/min until the solution is clear to obtain an aniline acid solution;
the molar ratio of aniline to acid in the aniline acid solution in the third ① is 1 (2-10);
②, adding the ammonium persulfate acid solution prepared in the first step ③ into an aniline acid solution, reacting for 20-26 h at the temperature of 0-5 ℃, and performing vacuum filtration to obtain a solid matter II, firstly, performing vacuum drying on the solid matter II for 20-24 h at the temperature of 55-65 ℃, then, grinding to obtain acid-doped polyaniline powder, and dissolving the acid-doped polyaniline powder into N, N-dimethylformamide to obtain an acid-doped polyaniline solution;
the volume ratio of the ammonium persulfate acid solution to the aniline acid solution in the third step ② is (0.5-1): 1;
the mass fraction of the acid-doped polyaniline solution in the step three ② is 1-20%;
fourthly, preparing the polyaniline film:
and (3) spin-coating or spraying the acid-doped polyaniline solution on the acid-doped poly-o-toluidine film obtained in the step two, naturally drying, and forming an acid-doped polyaniline film on the acid-doped poly-o-toluidine film to obtain the flexible polyaniline/poly-o-toluidine double-layer electrochromic film.
Fig. 1 is a schematic structural diagram of a flexible polyaniline/poly-o-toluidine double-layer electrochromic film according to a first embodiment, in which fig. 1 is a substrate, 2 is an acid-doped poly-o-toluidine film, and 3 is an acid-doped polyaniline film.
The principle and advantages of the embodiment are as follows:
the method adopts o-toluidine as a synthetic monomer of a functional material at the bottom layer of the flexible polyaniline/poly-o-toluidine composite electrochromic film, because substituent groups are introduced on a benzene ring, side reaction at ortho positions can be effectively prevented, and radical polymerization reaction at para positions is promoted, so that a long-chain conjugated structure is obtained, and meanwhile, methyl groups which are electron-donating groups and have small steric hindrance are introduced at the ortho positions of the benzene ring, so that the prepared film is more compact, the conductivity of a substrate is changed, and then a rough acid-doped polyaniline film is prepared on the basis, so that the construction of a double-layer composite structure is realized;
the flexible aniline/poly-o-toluidine composite electrochromic film prepared by the embodiment has high infrared regulation and control capability and good cycle stability, and can meet the demand of the national defense field on photo-thermal intelligent regulation and control;
and thirdly, the infrared emissivity of the flexible polyaniline/poly-o-toluidine double-layer electrochromic film prepared by the embodiment can reach 0.348.
The embodiment can obtain the flexible polyaniline/poly-o-toluidine double-layer electrochromic film.
The second embodiment is different from the first embodiment in that the acid used in the first step ① is dodecylbenzene sulfonic acid, camphorsulfonic acid, lauric acid, citric acid, hydrochloric acid with a mass fraction of 36% to 38%, perchloric acid with a mass fraction of 70% to 72%, or sulfuric acid with a mass fraction of 98%.
Third embodiment, the difference between the first embodiment and the second embodiment is that in the first step ①, deionized water is used as a solvent to prepare an acid solution with a concentration of 0.5 mol/L-1 mol/L.
Fourth embodiment the present embodiment is different from the first to third embodiments in that the molar ratio of the o-methylbenzylamine to the acid in the o-methylbenzylamine acid solution in the first step ② is 1 (2-5), and the other steps are the same as the first to third embodiments.
Fifth embodiment five the difference between this embodiment and the first to fourth embodiments is that the mass fraction of the acid-doped poly-o-toluidine solution in the first step ④ is 10% to 15%, and the other steps are the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the thickness of the acid-doped poly-o-toluidine film in the second step is 0.1-2 μm. The other steps are the same as those in the first to fifth embodiments.
Seventh embodiment mode, the difference between this embodiment mode and one of the first to sixth embodiment modes is that the molar ratio of aniline to acid in the aniline acid solution described in the third ① is 1 (4 to 6), and the other steps are the same as those in the first to sixth embodiment modes.
The eighth specific implementation mode is different from the first to seventh specific implementation modes in that in the third step ②, the ammonium persulfate acid solution prepared in the first step ③ is added into the aniline acid solution, the reaction is carried out for 20 to 24 hours at the temperature of 0 to 2 ℃, then vacuum filtration is carried out to obtain a solid matter II, the solid matter II is firstly dried for 22 to 24 hours at the temperature of 55 to 60 ℃ in vacuum, then grinding is carried out to obtain acid-doped polyaniline powder, the acid-doped polyaniline powder is dissolved into N, N-dimethylformamide to obtain an acid-doped polyaniline solution, and other steps are the same as the first to seventh specific implementation modes.
Ninth embodiment the difference between this embodiment and one of the first to eighth embodiments is that the mass fraction of the acid-doped polyaniline solution in the third step ② is 10% to 15%.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: the thickness of the flexible polyaniline/poly-o-toluidine double-layer electrochromic film in the fourth step is 0.5-4 μm. The other steps are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: a preparation method of a flexible polyaniline/poly-o-toluidine double-layer electrochromic film is completed according to the following steps:
firstly, preparing a poly-o-toluidine solution:
①, preparing an acid solution with the concentration of 1 mol/L by taking deionized water as a solvent;
the acid in the first step ① is sulfuric acid with the mass fraction of 98%;
②, adding distilled o-toluidine into the acid solution with the concentration of 1 mol/L prepared in the step one ①, and magnetically stirring at the stirring speed of 400r/min until the solution is clear to obtain an o-toluidine acid solution;
the mol ratio of o-methylbenzylamine to acid in the o-methylbenzylamine acid solution in the first step ② is 1: 2;
③, adding ammonium persulfate into the acid solution with the concentration of 1 mol/L prepared in the step one ①, and magnetically stirring for 10min at the stirring speed of 400r/min to obtain an ammonium persulfate acid solution;
the molar ratio of ammonium persulfate to acid in the ammonium persulfate acid solution in the first step ③ is 1: 5;
④, adding an ammonium persulfate solution into an o-methylbenzylamine acid solution, reacting at 0 ℃ for 24 hours, and carrying out vacuum filtration to obtain a solid substance I, firstly, carrying out vacuum drying on the solid substance I at 60 ℃ for 24 hours, then, grinding to obtain acid-doped poly-o-methylbenzylamine powder, and dissolving the acid-doped poly-o-methylbenzylamine powder into N, N-dimethylformamide to obtain an acid-doped poly-o-methylbenzylamine solution;
the volume ratio of the ammonium persulfate solution to the o-toluidine acid solution in the first step ④ is 1: 1;
the mass fraction of the acid-doped poly-o-toluidine solution in the first step ④ is 10%;
secondly, preparing a poly-o-toluidine film:
spin-coating the acid-doped poly-o-toluidine solution on the surface of a substrate, and naturally drying to form an acid-doped poly-o-toluidine film on the surface of the substrate;
the substrate in the second step is an ITO flexible conductive film;
the thickness of the acid-doped poly-o-toluidine film in the second step is 0.62 mu m;
thirdly, preparing a polyaniline solution:
①, adding distilled aniline into the acid solution with the concentration of 1 mol/L prepared in the step one ①, and magnetically stirring at the stirring speed of 400r/min until the solution is clear to obtain an aniline acid solution;
the molar ratio of aniline to acid in the aniline acid solution described in step three ① is 1: 5;
②, adding the ammonium persulfate acid solution prepared in the first step ③ into an aniline acid solution, reacting for 24 hours at the temperature of 0 ℃, and performing vacuum filtration to obtain a solid substance II;
the volume ratio of the ammonium persulfate acid solution to the aniline acid solution in the third step ② is 1: 1;
the mass fraction of the acid-doped polyaniline solution in the step three ② is 10%;
fourthly, preparing the polyaniline film:
spin-coating an acid-doped polyaniline solution on the acid-doped poly-o-toluidine film obtained in the second step, naturally drying, and forming an acid-doped polyaniline film on the acid-doped poly-o-toluidine film to obtain a flexible polyaniline/poly-o-toluidine double-layer electrochromic film;
the thickness of the flexible polyaniline/poly-o-toluidine double-layer electrochromic film in the fourth step is 1.35 mu m.
FIG. 2 is an SEM image of an acid-doped poly-o-toluidine thin film obtained in step two of the example;
as can be seen from FIG. 2, the thickness and presence of the acid-doped poly-o-toluidine film attached to the substrate;
FIG. 3 is an SEM image of a flexible polyaniline/poly-o-toluidine bilayer electrochromic film obtained in step four of the example;
as can be seen from fig. 3, the thickness and the appearance of the acid-doped poly-o-toluidine and polyaniline double-layer electrochromic film attached to the substrate;
fig. 4 is an infrared emissivity curve of the flexible polyaniline/poly-o-tolylamine double-layer electrochromic film obtained in step four of the embodiment, where 1 is-0.25V and 2 is 0.45V.
By combining the infrared emissivity curve of fig. 4 and the following two formulas, the adjustment amplitude of the infrared emissivity of the flexible polyaniline/poly-o-toluidine double-layer electrochromic film is calculated to be 0.348.
Figure BDA0001907931580000071
Figure BDA0001907931580000072
Where Emissivity is the infrared Emissivity, c1Is a first radiation constant (3.7418 × 10)8Wμm4m-2)，c2Is the second radiation constant (1.4388 × 10)4μ m K), λ is the wavelength and T is the temperature. The instrument used in the test was BRUKER GermanyCompany's Fourier Infrared Spectroscopy model VERTEX 70 with a test resolution of 4cm-1The number of scanning times is 32, and the scanning wave band is 2.5-25 μm.

Claims (10)

1. A preparation method of a flexible polyaniline/poly-o-toluidine double-layer electrochromic film is characterized in that the preparation method of the flexible polyaniline/poly-o-toluidine double-layer electrochromic film is completed according to the following steps:
firstly, preparing a poly-o-toluidine solution:
①, preparing an acid solution with the concentration of 0.1 mol/L-1 mol/L by taking deionized water as a solvent;
②, adding the distilled o-toluidine into the acid solution with the concentration of 0.1 mol/L-1 mol/L prepared in the step one ①, and magnetically stirring at the stirring speed of 200 r/min-400 r/min until the solution is clear to obtain an o-toluidine acid solution;
the mol ratio of the o-methylbenzylamine to the acid in the o-methylbenzylamine acid solution in the first step ② is 1 (2-10);
③, adding ammonium persulfate into the acid solution with the concentration of 0.1 mol/L-1 mol/L prepared in the step one ①, and magnetically stirring for 5-10 min at the stirring speed of 200-500 r/min to obtain an ammonium persulfate acid solution;
the molar ratio of ammonium persulfate to acid in the ammonium persulfate acid solution in the first step ③ is (1-1.5): 5;
④, adding an ammonium persulfate solution into an o-toluidine acid solution, reacting for 20-26 h at 0-5 ℃, and performing vacuum filtration to obtain a solid matter I, firstly, drying the solid matter I in vacuum for 20-24 h at 55-65 ℃, and then grinding to obtain acid-doped poly-o-toluidine powder;
the volume ratio of the ammonium persulfate solution to the o-toluidine acid solution in the first step ④ is (0.5-1): 1;
the mass fraction of the acid-doped poly-o-toluidine solution in the first step ④ is 1-20%;
secondly, preparing a poly-o-toluidine film:
spin-coating or spraying the acid-doped poly-o-toluidine solution on the surface of a substrate, and naturally drying to form an acid-doped poly-o-toluidine film on the surface of the substrate;
the substrate in the second step is an ITO flexible conductive film or a porous gold film;
thirdly, preparing a polyaniline solution:
①, adding distilled aniline into the acid solution with the concentration of 0.1 mol/L-1 mol/L prepared in the step one ①, and magnetically stirring at the stirring speed of 200 r/min-500 r/min until the solution is clear to obtain an aniline acid solution;
the molar ratio of aniline to acid in the aniline acid solution in the third ① is 1 (2-10);
②, adding the ammonium persulfate acid solution prepared in the first step ③ into an aniline acid solution, reacting for 20-26 h at the temperature of 0-5 ℃, and performing vacuum filtration to obtain a solid matter II, firstly, performing vacuum drying on the solid matter II for 20-24 h at the temperature of 55-65 ℃, then, grinding to obtain acid-doped polyaniline powder, and dissolving the acid-doped polyaniline powder into N, N-dimethylformamide to obtain an acid-doped polyaniline solution;
the volume ratio of the ammonium persulfate acid solution to the aniline acid solution in the third step ② is (0.5-1): 1;
the mass fraction of the acid-doped polyaniline solution in the step three ② is 1-20%;
fourthly, preparing the polyaniline film:
and (3) spin-coating or spraying the acid-doped polyaniline solution on the acid-doped poly-o-toluidine film obtained in the step two, naturally drying, and forming an acid-doped polyaniline film on the acid-doped poly-o-toluidine film to obtain the flexible polyaniline/poly-o-toluidine double-layer electrochromic film.
2. The method according to claim 1, wherein the acid in step one ① is dodecylbenzene sulfonic acid, camphorsulfonic acid, lauric acid, citric acid, hydrochloric acid with a mass fraction of 36-38%, perchloric acid with a mass fraction of 70-72%, or sulfuric acid with a mass fraction of 98%.
3. The method of claim 1, wherein the first step ① is performed by using deionized water as a solvent to prepare an acid solution with a concentration of 0.5 mol/L-1 mol/L.
4. The method for preparing a flexible polyaniline/poly-o-toluidine double-layer electrochromic film as claimed in claim 1, wherein the molar ratio of o-toluidine to acid in the o-toluidine acid solution in the step one ② is 1 (2-5).
5. The method according to claim 1, wherein the acid-doped poly (o-toluidine) solution in the first step ④ is 10-15% by weight.
6. The method according to claim 1, wherein the thickness of the acid-doped poly-o-toluidine film in step two is 0.1 μm to 2 μm.
7. The method for preparing the flexible polyaniline/poly-o-toluidine double-layer electrochromic film according to claim 1, wherein the molar ratio of aniline to acid in the aniline acid solution in the step three ① is 1 (4-6).
8. The method for preparing the flexible polyaniline/poly-o-toluidine double-layer electrochromic film according to claim 1, wherein the step three ② comprises the steps of adding the ammonium persulfate solution prepared in the step one ③ into the aniline acid solution, reacting at 0-2 ℃ for 20-24 h, performing vacuum filtration to obtain a solid substance II, performing vacuum drying on the solid substance II at 55-60 ℃ for 22-24 h, grinding to obtain acid-doped polyaniline powder, and dissolving the acid-doped polyaniline powder into N, N-dimethylformamide to obtain the acid-doped polyaniline solution.
9. The method for preparing a flexible polyaniline/poly-o-toluidine double-layer electrochromic film according to claim 1, wherein the mass fraction of the acid-doped polyaniline solution in step three ② is 10% to 15%.
10. The method according to claim 1, wherein the flexible polyaniline/poly-o-toluidine bilayer electrochromic film in step four has a thickness of 0.5 μm to 4 μm.
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