CN115196885B - CeO with multicolor and high cycle stability 2 PANI electrochromic film and preparation method thereof - Google Patents
CeO with multicolor and high cycle stability 2 PANI electrochromic film and preparation method thereof Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- 239000010413 mother solution Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
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- 241000579895 Chlorostilbon Species 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- 229910052876 emerald Inorganic materials 0.000 description 2
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- 238000002834 transmittance Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
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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
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
-
- 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
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/445—Organic continuous phases
-
- 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
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
-
- 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
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
Abstract
The invention discloses a CeO with multicolor and high cycle stability 2 A/PANI electrochromic film and its preparing process are prepared from the intermediate electrode potential CeO by silane coupling agent KH-550 2 Compounding with doped polyaniline to strengthen the interaction between RE metal ion and polyaniline chain, inhibit the oxidation and decomposition of polyaniline, raise the film circulation stability and raise CeO 2 The intermediate electron transition affects the spectral absorption of polyaniline in the visible light range, and the three colors of emerald-blackish green-reddish brown change reversibly. The electrochromic film prepared by the invention has a multi-color effect and excellent cycle stability.
Description
Technical Field
The invention relates to a novel electrochromic film material, in particular to a CeO with multicolor and high cycle stability 2 PANI electrochromic film.
Background
With the rapid development of economy and the improvement of living standard around the world, the demand of human beings for new intelligent materials is growing day by day, and higher and more urgent demands are put forward for the development and application of new materials. Electrochromic materials are a novel material which is widely researched and applied at present.
Electrochromic is a phenomenon that the optical properties of a material change stably and reversibly under the action of an external electric field. Electrochromic materials are classified according to electrochemical color-changing properties and structural sources, and can be mainly classified into inorganic electrochromic materials and organic electrochromic materials. The electrochromic material being based on transition metal oxides, e.g. WO 3 、TiO 2 、MoO 3 And the like, the material has good stability and excellent combination property with the conventional inorganic nonmetallic material, and the defects of single color change and poor cycle reversibility are overcome. The organic electrochromic material is mainly redox compound, metal organic chelate and conductive polymer, such as viologen, polyaniline, polythiophene, etc. Among them, polyaniline has reversible redox characteristics and excellent electrochromic properties, has a fast response speed in the visible near infrared region and a high optical contrast, and has the advantages of inexpensive and easily available raw materials, good cycle reversibility and rich color change, but has the disadvantage of difficulty in improving the cycle stability.
Therefore, a single electrochromic material is difficult to achieve the popularization and production requirements. At present, materials doped with luminescent ions are very widely focused in the scientific research field and the practical production field, rare earth metal ions have rich gradient energy levels, and can be considered to be combined with polyaniline, so that the polyaniline electrochromic film has more functional characteristics. The rare earth metal oxide is compounded with the conductive polymer, and the performance of the rare earth metal oxide can be effectively improved by playing the synergistic effect of the two materials, so that the rare earth metal oxide has huge research and application potential in the aspects of military camouflage, intelligent color-changing windows, electronic devices, energy fields and the like.
Although widely studied, polyaniline electrochromic materials still have some defects which restrict the production and application of the materials, and the main reasons are poor dissolution processability caused by a rigid molecular chain structure of polyaniline and poor cycle stability caused by oxidative degradation. The polyaniline electrochromic film prepared by the prior art has the effective cycle times of 1000-2000 times and the color is changed between yellow and green, so that the development of the polyaniline electrochromic material with high cycle stability, excellent processing performance and more color changes has great significance for promoting the practical application of polyaniline in industry.
Disclosure of Invention
The invention aims to solve the problems of complex process, high cost, poor cycle stability and single color change of the polyaniline film prepared by the prior method, and provides a CeO with multicolor high cycle stability 2 PANI electrochromic film and preparation method thereof.
The invention adopts the following technical scheme for realizing the purpose:
CeO with multicolor and high cycle stability 2 The preparation method of the PANI electrochromic film comprises the following steps:
step 1, synthesizing functionalized CeO by a hydrothermal method 2 ：
Mixing deionized water with absolute ethyl alcohol, and adding silane coupling agent KH-550 and CeO 2 Magnetically stirring for 20-30 min at a stirring speed of 800-1000 r/min, pouring the obtained mixed solution into a reaction kettle for reaction at 110-120 ℃ for 4-6 h, and obtaining the functionalized CeO after suction filtration, cleaning and drying 2 ；
Step 2, preparing a film forming mother solution by an emulsion method:
dissolving dodecylbenzene sulfonic acid in 1mol/L HCl solution, and adding aniline and the functionalized CeO 2 Magnetically stirring for 20-30 min at the stirring speed of 300-500 r/min at the low temperature of 0-5 ℃, dropwise adding 1mol/L initiator solution, stirring while dropwise adding, and continuously stirring for 10-12 h; filtering, filtering the filter cake with absolute ethanolAnd deionized water are respectively washed for 2-3 times, and absolute ethyl alcohol is added into the filter cake after washing to dissolve the filter cake, so as to obtain film forming mother liquor;
step 3, substrate pretreatment:
sequentially ultrasonically cleaning a substrate in acetone, absolute ethyl alcohol and deionized water, and drying to obtain a pretreated substrate;
step 4, preparing CeO by a dipping-pulling method 2 PANI electrochromic film:
vertically inserting the pretreated substrate into film-forming mother liquor, soaking for 10-15 s, uniformly extracting the substrate, naturally airing to obtain multi-color CeO with high cycle stability 2 PANI electrochromic film.
Further, in step 1, the silane coupling agent KH-550 and the CeO 2 The molar ratio of (2) is 1:4.
Further, in step 1, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:3.
Further, in the step 2, the initiator is one of ammonium persulfate, potassium persulfate and ferric trichloride.
Further, in step 2, the dodecylbenzenesulfonic acid is mixed with HCl, aniline and functionalized CeO 2 The molar ratio of the initiator is 1:1:2:0.5:2.
Further, in the step 2, the dripping speed of the initiator is 15-20 drops/min.
Further, in the step 2, the mass ratio of the filter cake after cleaning to the absolute ethyl alcohol is 2:1, and the dynamic viscosity of the obtained film forming mother liquor is 170-192 cp.
Further, in step 3, the substrate is ITO glass.
Further, in the step 4, the lifting speed of the substrate is 3mm/s.
The invention adopts inorganic/organic material composite preparation means, and uses dodecyl benzene sulfonic acid as an emulsifying agent and doping acid, thereby improving the dissolution processability of the product; adopting silane coupling agent KH-550 to make CeO of intermediate electrode potential 2 Compounding with doped polyaniline to strengthen the interaction between RE metal ion and polyaniline chain,inhibiting the oxidative decomposition of polyaniline and improving the cycling stability of the film; ceO (CeO) 2 The intermediate electron transition affects the spectral absorption of polyaniline in the visible light range, and the three colors of emerald-blackish green-reddish brown change reversibly.
Compared with the prior art, the invention has the beneficial effects that:
1. the CeO with multicolor and high cycle stability of the invention 2 The PANI electrochromic film is prepared into a film forming mother solution by adopting an emulsion method, solves the problem of poor dissolution processability caused by a rigid molecular structure of polyaniline, can be matched with coating means such as a dipping-pulling method, a spin coating method, a knife coating method and the like, is suitable for preparing the electrochromic film and related devices in a large area, has simple production process and small investment on production equipment, and is convenient for process expansion production.
2. The CeO with multicolor and high cycle stability of the invention 2 The PANI electrochromic film generates new color change by compounding rare earth metal elements with intermediate electrode potential with polyaniline to influence the electronic transition process during electrochromic, can realize the reversible change of emerald-blackish green-reddish brown three colors under the voltage of-0.6V to +1.0V, and presents multicolor effect: when the voltage reaches-0.2V, the film is emerald; when the voltage reaches +0.4V, the film is dark green; when the voltage reaches +0.6V, the film is reddish brown.
3. The CeO with multicolor and high cycle stability of the invention 2 The PANI electrochromic film utilizes a silane coupling agent to chemically combine an inorganic material and an organic material, and can effectively inhibit the oxidative degradation of polyaniline through intermolecular forces, so that the stability of the electrochromic material is improved, and after 5000 coloring-fading cycles, the film still keeps 90% of electrochemical activity, and has good cycling stability.
4. The invention relates to a multi-color CeO with high cycle stability 2 The PANI electrochromic film has light absorption and transmission adjustability under the action of an electric field, can be applied to the field of photovoltaic energy conservation, changes the light absorption and reflection effects, achieves the effect of being warm in winter and cool in summer indoors, reduces energy consumption, and has important significance in the aspect of protecting the environment.
Drawings
FIG. 1 shows CeO 2 XRD pattern of PANI electrochromic film;
FIG. 2 is CeO 2 Cyclic voltammogram of PANI electrochromic film;
FIG. 3 is CeO 2 Cycling stability test results of PANI electrochromic films;
FIG. 4 is CeO 2 The ultraviolet-visible light transmission spectrum of the/PANI electrochromic film corresponds to voltages of-0.4V, -0.2V, 0V, +0.2V, +0.4V, +0.6V, +0.8V in order from top to bottom.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
In this example, a multi-color CeO with high cycle stability was prepared as follows 2 PANI electrochromic film:
step 1, synthesizing functionalized CeO by a hydrothermal method 2 ：
Mixing deionized water and absolute ethyl alcohol in a volume ratio of 1:3, and adding a silane coupling agent KH-550 and CeO in a molar ratio of 1:4 2 Magnetically stirring for 30min at a stirring speed of 1000r/min, pouring the obtained mixed solution into a reaction kettle for reaction at 110 ℃ for 4h, and obtaining the functionalized CeO after suction filtration, cleaning and drying 2 。
Step 2, preparing a film forming mother solution by an emulsion method:
dissolving dodecylbenzene sulfonic acid in 1mol/L HCl solution, and adding aniline and functionalized CeO 2 Magnetically stirring for 30min at a stirring speed of 500r/min at a low temperature of 5 ℃, dropwise adding 1mol/L ammonium persulfate initiator solution at a dripping speed of 15 drops/min, stirring while dropwise adding, and continuously stirring for 12h; after suction filtration, the filter cake is respectively washed 3 times by absolute ethyl alcohol and deionized water, and the washed filter cake is dissolved by absolute ethyl alcohol (the mass ratio of the filter cake to the absolute ethyl alcohol is 2:1) to obtain film-forming mother liquor with the dynamic viscosity of 170 cp; wherein: dodecyl benzene sulfonic acid, hydrochloric acid and benzeneAmine and functionalized CeO 2 The molar ratio of the ammonium persulfate initiator is 1:1:2:0.5:2.
Step 3, substrate pretreatment:
and sequentially ultrasonically cleaning ITO glass serving as a substrate in acetone, absolute ethyl alcohol and deionized water, and drying to obtain a pretreated substrate.
Step 4, preparing CeO by a dipping-pulling method 2 PANI electrochromic film:
vertically inserting the pretreated substrate into film-forming mother liquor, soaking for 15s, extracting the substrate at a constant speed of 3mm/s, naturally airing to obtain multi-color CeO with high cycle stability 2 PANI electrochromic film.
CeO with high cycle stability for multicolor obtained in this example 2 The performance of the/PANI electrochromic film was tested and analyzed as follows, with electrochemical correlation testing at 1mol/L LiClO 4 In PC electrolyte solution:
and (3) microscopic morphology analysis: polyaniline fiber diameter is about 2-4 μm, is in staggered branch shape, provides channel for ion implantation/separation in oxidation-reduction process, ceO 2 The particles are attached to the surface of polyaniline by a silane coupling agent, and the overall thickness of the film prepared by the dip-coating method is about 153 mu m.
Composition structural analysis: FIG. 1 is a multi-color CeO with high cycling stability 2 XRD pattern of the PANI electrochromic film. The typical broad amorphous diffraction peak of the eigenstate polyaniline is more sharp and has higher intensity at 2θ=15°, 20 °, and the corresponding pdf#75-0076CeO appears at 2θ=28.6 °, 33.4 °, 47.8 °, 56.7 °, 59.4 °, 69.7 °, 77.1 ° 2 The diffraction peaks characteristic of the (111), (200), (220), (311), (222), (400), (331) crystal planes indicate CeO 2 Successfully complex with polyaniline and functionalize CeO 2 the-NH group in (a) provides a reaction site for the attachment of aniline ions, and the attached monomers provide nucleation sites for the further growth of the polymer, so that the molecular chain of polyaniline has better orientation, shows higher crystallinity and is beneficial to the injection/ejection of ions in the color-changing reaction.
Electrochemical performance analysis: FIG. 2 shows a multi-color CeO with high cycle stability 2 Cyclic voltammogram of PANI electrochromic film. Curve 1 represents a scanning speed of 0.01V/s, curve 2 represents a scanning speed of 0.05V/s, curve 3 represents a scanning speed of 0.1V/s, two oxidation peaks appear near-0.3V and +0.75v, corresponding to the two processes of the reduced state (LES) transition of polyaniline to the semi-oxidized state (ES) and the semi-oxidized state (ES) transition to the fully oxidized state (PS), and the two oxidation peaks correspond to the two reduction peaks at-0.2V and +0.5V, respectively, in the upper half of the cyclic voltammetry curve, forming a cyclic reversible process. When the scanning speed is increased from 0.01V/s to 0.1V/s, the corresponding current at the same potential is also increased linearly, which shows that CeO 2 The charge-discharge response of the/PANI electrode is highly reversible.
FIG. 3 is a multi-color CeO with high cycling stability 2 Cycling stability test results of PANI electrochromic thin film electrode. After the external electric field is applied, the oxidative degradation of polyaniline greatly affects the cycle service life of the film, and CeO is attached to the surface 2 Is subjected to CeO 2 And the oxidation degradation of polyaniline can be effectively inhibited under the action of intermolecular force by connecting the silane coupling agents KH-550, and the film still maintains 90% of electrochemical activity after 5000 coloring-fading cycles under the applied voltage of-0.6V to +1.0V.
Electrochromic performance analysis: FIG. 4 is a multi-color CeO with high cycling stability 2 LiClO of/PANI electrochromic film electrode at 1mol/L 4 Ultraviolet-visible light transmission spectrum measured in PC electrolyte solution. Under the action of negative potential of-0.4V-0V, lithium ion extraction occurs, and polyaniline obtains electrons in a reduced state, ce 4+ Reduction to Ce 3+ The transition energy generated by the transition of the valence electron between different energy levels influences the absorption of the polyaniline spectrum in the visible light range, so that the light transmittance of the film is high within the wavelength range of 570-600 nm to be emerald; when the potential is increased from 0V to +0.4V, lithium ion implantation occurs, polyaniline loses electrons and is in an intermediate oxidation state, a transmittance peak on a curve moves towards a wavelength reduction direction, and a film is dark green; when the potential reaches a higher potential of +0.6V, the polyaniline is oxidizedThe state is obviously absorbed in the whole visible light region and is reddish brown under the influence of transition energy generated by the valence state change of Ce ions.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (8)
1. CeO with multicolor and high cycle stability 2 The preparation method of the PANI electrochromic film is characterized by comprising the following steps:
step 1, synthesizing functionalized CeO by a hydrothermal method 2 ：
Mixing deionized water with absolute ethyl alcohol, and adding silane coupling agent KH-550 and CeO 2 Magnetically stirring for 20-30 min at a stirring speed of 800-1000 r/min, pouring the obtained mixed solution into a reaction kettle for reaction at 110-120 ℃ for 4-6 h, and obtaining the functionalized CeO after suction filtration, cleaning and drying 2 The method comprises the steps of carrying out a first treatment on the surface of the The silane coupling agent KH-550 and the CeO 2 The molar ratio of (2) is 1:4;
step 2, preparing a film forming mother solution by an emulsion method:
dissolving dodecylbenzene sulfonic acid in 1mol/L HCl solution, and adding aniline and the functionalized CeO 2 Magnetically stirring for 20-30 min at the stirring speed of 300-500 r/min at the low temperature of 0-5 ℃, dropwise adding 1mol/L initiator solution, stirring while dropwise adding, and continuously stirring for 10-12 h; after suction filtration, the filter cake is respectively washed for 2-3 times by absolute ethyl alcohol and deionized water, and the washed filter cake is dissolved by the absolute ethyl alcohol to obtain film forming mother liquor; the dodecylbenzene sulfonic acid, HCl, aniline and functionalized CeO 2 The molar ratio of the initiator is 1:1:2:0.5:2;
step 3, substrate pretreatment:
sequentially ultrasonically cleaning a substrate in acetone, absolute ethyl alcohol and deionized water, and drying to obtain a pretreated substrate;
step 4, preparing CeO by a dipping-pulling method 2 PANI electrochromic film:
vertically inserting the pretreated substrate into film-forming mother liquor, soaking for 10-15 s, uniformly extracting the substrate, naturally airing to obtain multi-color CeO with high cycle stability 2 PANI electrochromic film.
2. A multi-color CeO of high cyclic stability according to claim 1 2 The preparation method of the PANI electrochromic film is characterized by comprising the following steps of: in the step 1, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:3.
3. A multi-color CeO of high cyclic stability according to claim 1 2 The preparation method of the PANI electrochromic film is characterized by comprising the following steps of: in the step 2, the initiator is one of ammonium persulfate, potassium persulfate and ferric trichloride.
4. A multi-color CeO of high cyclic stability according to claim 1 2 The preparation method of the PANI electrochromic film is characterized by comprising the following steps of: in the step 2, the dripping speed of the initiator is 15-20 drops/min.
5. A multi-color CeO of high cyclic stability according to claim 1 2 The preparation method of the PANI electrochromic film is characterized by comprising the following steps of: in the step 2, the mass ratio of the filter cake after cleaning to the absolute ethyl alcohol is 2:1, and the dynamic viscosity of the obtained film forming mother liquor is 170-192 cp.
6. A multi-color CeO of high cyclic stability according to claim 1 2 The preparation method of the PANI electrochromic film is characterized by comprising the following steps of: in the step 3, the substrate is ITO glass.
7. A multi-color CeO of high cyclic stability according to claim 1 2 The preparation method of the PANI electrochromic film is characterized by comprising the following steps of: in the step 4, the lifting speed of the substrate is 3mm/s.
8. A multi-color CeO of high cycle stability prepared by the method of any one of claims 1 to 7 2 PANI electrochromic film.
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