CN115746357B - Polyaniline film with micro-nano hierarchical structure based on styrene-acrylic emulsion template - Google Patents
Polyaniline film with micro-nano hierarchical structure based on styrene-acrylic emulsion template Download PDFInfo
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Abstract
The invention provides a preparation method of a polyaniline film with a micro-nano hierarchical structure based on a styrene-acrylic emulsion template, which comprises the following steps: s1, preparing styrene-acrylic emulsion with a certain glass transition temperature; s2, forming an emulsion film on the conductive substrate by using the styrene-acrylic emulsion, and drying under certain conditions to obtain a modified electrode with micro cracks; s3, performing electrodeposition on the electrode to obtain a sample, and performing emulsion template removal treatment on the sample to obtain a polyaniline film; according to the invention, a styrene-acrylic emulsion template is introduced on a conductive substrate, a substrate with a special conductive network is constructed, electrodeposition of a polyaniline electrochromic material is carried out, and microscopic morphology regulation and control of the polyaniline material are carried out by cooperatively utilizing a template effect and a material growth strategy, so that the high-response electrochromic polyaniline film material with high porosity and a micro-nano hierarchical structure is obtained.
Description
Technical Field
The invention relates to a polyaniline electrochromic energy-storage film, in particular to a polyaniline film with a micro-nano hierarchical structure based on a styrene-acrylic emulsion template and a preparation method thereof.
Background
Electrochromic refers to the change in optical properties (transmittance, reflectance or absorptivity) of a material under the action of an electric field, exhibiting stable, reversible changes in color and transparency. Among the electrochromic materials, polyaniline has the advantages of simple synthesis, low production cost, high conductivity, good chemical stability and the like, and can generate electrochromic phenomena through rapid and reversible doping/dedoping reactions in the whole bulk phase. Meanwhile, the electrochromic and super-capacitor phenomena depend on the oxidation-reduction reaction of the materials, and the energy storage effect is accompanied in the process of changing the color of the materials in the process of ion implantation/extraction, so that the polyaniline material has wide application prospect and is a hot spot subject for research in the current multi-color electrochromic and energy storage fields.
However, in the electrochemical reaction process of polyaniline, repeated doping/dedoping reactions occur on molecular chains along with intercalation and deintercalation of ions, so that the volume of polyaniline expands and contracts, the color-changing capability of polyaniline is obviously attenuated after the polyaniline undergoes multiple electrochemical cycles, and the cycling stability is poor. In addition, the dense material structure also causes difficulty in ion diffusion in doping/dedoping, thereby affecting ion transport kinetics, resulting in an increase in color change response time. Therefore, to increase the response speed and reduce the structural stress during the electrochemical reaction, it is generally necessary to construct a regular and ordered molecular arrangement to promote the transition of electrons between molecular chains, and at the same time, a loose structure with high porosity can provide an advantageous channel for ion deintercalation.
There is a need to design a polyaniline electrochromic film material with high porosity and micro-nano hierarchical structure, high response speed and excellent pseudocapacitance characteristics to overcome the above problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a polyaniline film with a micro-nano hierarchical structure based on a styrene-acrylic emulsion template and a preparation method thereof, and solves the problem that the appearance of the traditional polyaniline electrochromic energy storage material is relatively compact.
The invention is realized in the following way:
the invention provides a preparation method of a polyaniline film with a micro-nano hierarchical structure based on a styrene-acrylic emulsion template, which comprises the following steps:
s1, preparing styrene-acrylic emulsion with a certain glass transition temperature;
s2, forming an emulsion film on the conductive substrate by using the styrene-acrylic emulsion, and drying under certain conditions to obtain a modified electrode with micro cracks;
and S3, performing electrodeposition on the modified electrode to obtain a sample, and performing emulsion template removal treatment on the sample to obtain the polyaniline film.
According to the method, a styrene-acrylic emulsion template is introduced on a conductive substrate, and in the emulsion drying film forming process, stress is generated due to solvent volatilization, so that microscopic cracks are generated on the surface of an emulsion film, an electrode with a special conductive network is constructed, electrodeposition of a polyaniline electrochromic material is carried out subsequently, a template effect and a material growth strategy are cooperatively utilized, polyaniline nucleates and grows on the conductive network of the electrode, and then the microscopic morphology of the polyaniline material is regulated and controlled.
Further, in the step S1, the glass transition temperature of the styrene-acrylic emulsion is 40-60 ℃.
Further, in step S1, monomers used for preparing the styrene-acrylic emulsion are acrylic acid, hydroxypropyl methacrylate, methyl methacrylate, butyl acrylate, and styrene.
Further, in step S2, spin coating is performed on the conductive substrate, and after repeating the coating, an emulsion film is obtained and dried at a drying temperature of 70 ℃. The film forming environment and the film forming temperature can control the volatilization rate of the solvent, the faster the solvent volatilizes, the more easily the stress is generated, thereby generating cracks, when the film forming temperature of the styrene-acrylic emulsion is higher than the glass transition temperature, the film can be formed on the conductive substrate, and the drying temperature is preferably 70 ℃.
Further, the conductive substrate is one of ITO glass, FTO glass, or conductive PET.
Further, in the step S3, a three-electrode system is adopted for electrodeposition, the modified electrode in the step S2 is a working electrode, the platinum sheet is a counter electrode, and Ag/AgCl is a reference electrode.
Further, in step S3, the electrodeposition solution is a mixed solution of hydrochloric acid or sulfuric acid, aniline, and deionized water.
Further, in step S3, a method of combining cyclic voltammetry and potentiostatic deposition, or a method of combining cyclic voltammetry and galvanostatic deposition is adopted in the electrodeposition process.
The upper limit scanning voltage and the upper limit scanning current of the cyclic voltammetry are set in the electrodeposition process to be improved simultaneously, the generation of polyaniline salt is effectively promoted in the cyclic voltammetry electrodeposition process, the steric hindrance formed by a long chain of polyaniline is reduced, the dissolution rate of polyaniline in an electrolyte is ensured to be smaller than the deposition rate of polyaniline, and a polyaniline film can be formed stably. But the polyaniline film prepared by the cyclic voltammetry electrodeposition technology has irregular surface and loose inter-particle contact.
In the constant potential deposition process, aniline is continuously polymerized on the substrate, so that a compact and flat surface is obtained, and when the deposition time is not too long, the deposited film is mainly in a particle shape. The polyaniline film prepared by constant current deposition has smaller nano particle size and has the characteristics of uniformity, compactness and smoothness. The nano-particle modified micro-nano hierarchical structure can be obtained on the loose polyaniline material by combining cyclic voltammetry with potentiostatic deposition or combining cyclic voltammetry with galvanostatic deposition technology, so that the active site of electrochemical reaction is increased.
Further, in step S3, the emulsion template removal process includes: the sample was rinsed with ethanol and immersed in a mixed solution of N, N-dimethylformamide and toluene for 12 hours, the mixed solution being replaced every 4 hours, the volume ratio of N, N-dimethylformamide to toluene being 1:1.
The invention also provides the polyaniline film prepared by the method, has a micro-nano hierarchical structure with high porosity, and is a multi-color electrochromic energy storage material.
The invention has the following beneficial effects:
1. according to the invention, the electrode modified by the styrene-acrylic emulsion film is used as a template, and the nucleation and growth positions of polyaniline on the electrode are regulated by regulating and controlling microscopic cracks of the styrene-acrylic emulsion film, so that a high-porosity micro-nano hierarchical structure is obtained;
2. according to the invention, through the combination of the cyclic voltammetry and the constant potential deposition method or the electrodeposition method of the combination of the cyclic voltammetry and the constant current deposition method, a film material with good adhesive force can be obtained, and meanwhile, a micro-nano hierarchical structure can be obtained, so that the electrochemical reaction active site is increased, and the response speed is improved;
3. the high-porosity micro-nano hierarchical structure of the polyaniline film prepared by the method is beneficial to ion injection and extraction, slows down structural stress generated by electrochemical reaction, and improves electrochemical reaction stability.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image at 500nm of a polyaniline film prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a polymer modified FTO electrode at 100 μm in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a film sample formed by electrodeposition in example 1 of the present invention at 100 μm;
FIG. 4 is a scanning electron microscope image at 500nm of the polyaniline film prepared in comparative example 1 of the present invention;
FIG. 5 is a scanning electron microscope image at 500nm of the polyaniline film prepared in comparative example 2 of the present invention;
FIG. 6 is a scanning electron microscope image at 500nm of the polyaniline film prepared in example 2 of the present invention;
FIG. 7 is a scanning electron microscope image of a polymer modified FTO electrode at 500nm according to comparative example 3 of the present invention;
FIG. 8 is a graph showing the morphology of the polyaniline film produced in example 1 of the present invention at various voltages;
FIG. 9 is a graph showing the spectrum of the polyaniline film obtained in example 1 of the present invention at various voltages;
FIG. 10 shows constant current charge and discharge curves of the polyaniline film prepared in example 1 of the present invention at different current densities;
FIG. 11 is a graph showing the area specific capacity comparison of the polyaniline films produced in comparative example 1 and example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing a polyaniline electrochromic film based on a styrene-acrylic emulsion template, which comprises the following steps:
step 1, preparing an emulsifier solution: weighing 70g of deionized water, adding into a 250ml beaker, adding 0.3g of sodium bicarbonate, 1.0g of sodium dodecyl and 2.0g of alkylphenol ethoxylate, stirring and dissolving, pouring into a four-neck flask, starting electric stirring, and heating to 80-82 ℃ in a water bath;
preparing a monomer solution: each monomer was 2.0g acrylic acid, 3.0g hydroxypropyl methacrylate, 49.8g methyl methacrylate, 36.4g butyl acrylate, and 25.0g styrene;
preparing a supplementary initiator solution: 0.3g ammonium persulfate was dissolved in 30g deionized water.
And slowly dropwise adding 10.0g of monomer solution into the four-neck flask, preserving heat for 20 minutes after blue light appears, respectively dropwise adding the residual monomer solution and the supplementary initiator solution by using two constant pressure funnels, and finishing the dropwise adding within 2 hours. The whole polymerization process keeps the reaction temperature at 80-82 ℃, after the dripping is finished, the temperature is kept for 0.5h, after the dripping is cooled to 50 ℃, ammonia water is used for adjusting the pH value of the emulsion to 7.0-8.0, and the styrene-acrylic emulsion with the glass transition temperature of 50 ℃ is obtained;
step 3, uniformly coating the styrene-acrylic emulsion on the surface of the FTO conductive glass by adopting a spin coating process, wherein spin coating parameters are 500rpm and 10s at a low speed; after repeated spin coating at a high speed of 3000rpm for 20 seconds, placing the FTO glass coated with the emulsion film in a 70 ℃ oven for drying for standby, and obtaining the polymer modified FTO electrode;
step 4, adopting a three-electrode system, and taking the polymer modified FTO electrode as working electricityAnd (3) performing electrochemical deposition by taking a pole and a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode to obtain the polyaniline film with the micro-nano hierarchical structure. Wherein the electro-deposition solution is a mixed solution of aniline, sulfuric acid and deionized water, the electro-deposition adopts a method of combining cyclic voltammetry and potentiostatic deposition, the voltage range is between 0 and 1.0V, and the sweeping speed is 50 mV.s -1 Depositing for 3 cycles by cyclic voltammetry, and then depositing for 15min at 0.75V by potentiostatic deposition;
and 5, after the electrodeposition is finished, washing the film sample by using ethanol, soaking the film sample in a mixed solution of N, N-dimethylformamide and toluene for 12 hours, and replacing the soaking solution every 4 hours, wherein the volume ratio of the N, N-dimethylformamide to the toluene is 1:1. And finally, placing the sample into an oven to be dried at 40 ℃ to obtain the polyaniline electrochromic film with the high-porosity micro-nano hierarchical structure.
Example 2
Preparing a polyaniline electrochromic film based on a styrene-acrylic emulsion template, which comprises the following steps:
step 1, preparing an emulsifier solution: weighing 70g of deionized water, adding into a 250ml beaker, adding 0.3g of sodium bicarbonate, 1.0g of sodium dodecyl and 2.0g of alkylphenol ethoxylate, stirring and dissolving, pouring into a four-neck flask, starting electric stirring, and heating to 80-82 ℃ in a water bath;
preparing a monomer solution: each monomer was 2.0g acrylic acid, 3.0g hydroxypropyl methacrylate, 44.76g methyl methacrylate, 25.34g butyl acrylate, and 25.0g styrene;
preparing a supplementary initiator solution: 0.3g ammonium persulfate was dissolved in 30g deionized water;
and slowly dropwise adding 10.0g of monomer solution into the four-neck flask, preserving heat for 20 minutes after blue light appears, respectively dropwise adding the residual monomer solution and the supplementary initiator solution by using two constant pressure funnels, and finishing the dropwise adding within 2 hours. The whole polymerization process keeps the reaction temperature at 80-82 ℃, after the dripping is finished, the temperature is kept for 0.5h, after the dripping is cooled to 50 ℃, ammonia water is used for adjusting the pH value of the emulsion to 7.0-8.0, and the styrene-acrylic emulsion with the glass transition temperature of 40 ℃ is obtained;
step 3, uniformly coating the styrene-acrylic emulsion on the surface of the FTO conductive glass by adopting a spin coating process, wherein spin coating parameters are 300rpm and 10s at a low speed; after repeated spin coating at a high speed of 2000rpm for 20 seconds, placing the FTO glass coated with the emulsion in a 70 ℃ oven for drying for standby, and obtaining a polymer modified FTO electrode;
and 4, adopting a three-electrode system, and performing electrochemical deposition by taking a polymer modified FTO electrode as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode to obtain the polyaniline film with the micro-nano hierarchical structure. Wherein the electrodeposition solution is a mixed solution of aniline, hydrochloric acid and deionized water, the electrodeposition adopts a method of combining cyclic voltammetry and constant current deposition, firstly, 5 cycles are deposited between-0.2V and 0.8V by the cyclic voltammetry, and the sweeping speed is 50 mV.s -1 Then using constant current deposition method to make deposition current density be 0.15mA cm -2 Deposition time is 200s;
and 5, after the electrodeposition is finished, washing the film sample by using ethanol, soaking the film sample in a mixed solution of N, N-dimethylformamide and toluene for 12 hours, and replacing the soaking solution every 4 hours, wherein the volume ratio of the N, N-dimethylformamide to the toluene is 1:1. And finally, placing the sample into an oven to be dried at 40 ℃ to obtain the polyaniline electrochromic film with high porosity and micro-nano hierarchical structure.
Example 3
Preparing a polyaniline electrochromic film based on a styrene-acrylic emulsion template, which comprises the following steps:
step 1, preparing an emulsifier solution: weighing 70g of deionized water, adding into a 250ml beaker, adding 0.3g of sodium bicarbonate, 1.0g of sodium dodecyl and 2.0g of alkylphenol ethoxylate, stirring and dissolving, pouring into a four-neck flask, starting electric stirring, and heating to 80-80 ℃ in a water bath;
preparing a monomer solution: each monomer was 2.0g acrylic acid, 3.0g hydroxypropyl methacrylate, 54.5g methyl methacrylate, 15.5g butyl acrylate, and 25.0g styrene;
preparing a supplementary initiator solution: 0.3g ammonium persulfate was dissolved in 30g deionized water;
and slowly dropwise adding 10.0g of monomer solution into the four-neck flask, preserving heat for 20 minutes after blue light appears, respectively dropwise adding the residual monomer solution and the supplementary initiator solution by using two constant pressure funnels, and finishing the dropwise adding within 2 hours. The whole polymerization process keeps the reaction temperature at 80-82 ℃, after the dripping is finished, the temperature is kept for 0.5h, after the dripping is cooled to 50 ℃, ammonia water is used for adjusting the pH value of the emulsion to 7.0-8.0, and the styrene-acrylic emulsion with the glass transition temperature of 60 ℃ is obtained;
step 3, uniformly coating the styrene-acrylic emulsion on the surface of the FTO conductive glass by adopting a spin coating process, wherein spin coating parameters are 300rpm and 10s at a low speed; after repeated spin coating at a high speed of 3000rpm for 20 seconds, placing the FTO glass coated with the emulsion in a 70 ℃ oven for drying for standby, and obtaining the polymer modified FTO electrode;
and 4, adopting a three-electrode system, and performing electrochemical deposition by taking a polymer modified FTO electrode as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode to obtain the polyaniline film with the micro-nano hierarchical structure. Wherein the electrodeposition liquid is a mixed solution of aniline, hydrochloric acid and deionized water, the electrodeposition adopts a method of combining cyclic voltammetry and potentiostatic deposition, and the deposition speed is 50 mV.s in 5 cycles between 0 and 1.0V by using the cyclic voltammetry -1 Then using a constant potential deposition method to deposit the metal oxide film at a voltage of 0.75V for 10min;
and 5, after the electrodeposition is finished, washing the film sample by using ethanol, soaking the film sample in a mixed solution of N, N-dimethylformamide and toluene for 12 hours, and replacing the soaking solution every 4 hours, wherein the volume ratio of the N, N-dimethylformamide to the toluene is 1:1. And finally, placing the sample into an oven to be dried at 40 ℃ to obtain the polyaniline electrochromic film with high porosity and micro-nano hierarchical structure.
Comparative example 1
The method does not introduce a styrene-acrylic emulsion template, directly grows a polyaniline electrochromic film on the FTO conductive substrate, and adopts the following steps:
step 1, respectively ultrasonically cleaning FTO transparent conductive glass in acetone, ethanol and deionized water in sequence, removing dust and grease on the surface, and drying for later use;
and 2, performing electrochemical deposition by adopting a three-electrode system, taking FTO transparent conductive glass as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode to obtain the polyaniline film. Wherein the electrodeposition liquid is a mixed solution of aniline, hydrochloric acid and deionized water, the electrodeposition adopts a method of combining cyclic voltammetry and potentiostatic deposition, and the deposition speed is 50 mV.s in 3 cycles between 0 and 1.0V by using the cyclic voltammetry -1 Then using a constant potential deposition method to deposit the metal oxide film at a voltage of 0.75V for 15min; and finally, placing the sample into an oven to be dried at 40 ℃ to obtain the polyaniline electrochromic film directly deposited on the FTO transparent conductive substrate.
Comparative example 2
Preparing a polyaniline electrochromic film based on a styrene-acrylic emulsion template, which comprises the following steps:
step 1, preparing an emulsifier solution: weighing 70g of deionized water, adding into a 250ml beaker, adding 0.3g of sodium bicarbonate, 1.0g of sodium dodecyl and 2.0g of alkylphenol ethoxylate, stirring and dissolving, pouring into a four-neck flask, starting electric stirring, and heating to 80-82 ℃ in a water bath;
preparing a monomer solution: each monomer was 2.0g acrylic acid, 3.0g hydroxypropyl methacrylate, 54.5g methyl methacrylate, 15.5g butyl acrylate, and 25.0g styrene;
preparing a supplementary initiator solution: 0.3g ammonium persulfate was dissolved in 30g deionized water;
and slowly dropwise adding 10.0g of monomer solution into the four-neck flask, preserving heat for 20 minutes after blue light appears, respectively dropwise adding the residual monomer solution and the supplementary initiator solution by using two constant pressure funnels, and finishing the dropwise adding within 2 hours. The whole polymerization process keeps the reaction temperature at 80-82 ℃, after the dripping is finished, the temperature is kept for 0.5h, after the dripping is cooled to 50 ℃, ammonia water is used for adjusting the pH value of the emulsion to 7.0-8.0, and the styrene-acrylic emulsion with the glass transition temperature of 60 ℃ is obtained;
step 3, uniformly coating the styrene-acrylic emulsion on the surface of the FTO conductive glass by adopting a spin coating process, wherein spin coating parameters are 300rpm and 10s at a low speed; after repeated spin coating at a high speed of 3000rpm for 20 seconds, placing the FTO glass coated with the emulsion in a 70 ℃ oven for drying for standby, and obtaining the polymer modified FTO electrode;
and 4, adopting a three-electrode system, and performing electrochemical deposition by taking a polymer modified FTO electrode as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode to obtain the polyaniline film with the micro-nano hierarchical structure. Wherein the electrodeposition liquid is a mixed solution of aniline, hydrochloric acid and deionized water, the electrodeposition adopts a cyclic voltammetry electrodeposition method, 5 cycles are deposited within the voltage range of-0.2 to 0.8V, and the sweeping speed is 50 mV.s -1 ；
And 5, after the electrodeposition is finished, washing the film sample by using ethanol, soaking the film sample in a mixed solution of N, N-dimethylformamide and toluene for 12 hours, and replacing the soaking solution every 4 hours, wherein the volume ratio of the N, N-dimethylformamide to the toluene is 1:1. And finally, placing the sample into an oven to be dried at 40 ℃ to obtain the polyaniline electrochromic film with high porosity.
Comparative example 3
Preparing a styrene-acrylic emulsion template with a glass transition temperature of 70 ℃, and adopting the following steps:
step 1, preparing an emulsifier solution: weighing 70g of deionized water, adding into a 250ml beaker, adding 0.3g of sodium bicarbonate, 1.0g of sodium dodecyl and 2.0g of alkylphenol ethoxylate, stirring and dissolving, pouring into a four-neck flask, starting electric stirring, and heating to 80-82 ℃ in a water bath;
preparing a monomer solution: each monomer was 2.0g acrylic acid, 3.0g hydroxypropyl methacrylate, 58.98g methyl methacrylate, 11.02g butyl acrylate, and 25.0g styrene;
preparing a supplementary initiator solution: 0.3g ammonium persulfate was dissolved in 30g deionized water;
and slowly dropwise adding 10.0g of monomer solution into the four-neck flask, preserving heat for 20 minutes after blue light appears, respectively dropwise adding the residual monomer solution and the supplementary initiator solution by using two constant pressure funnels, and finishing the dropwise adding within 2 hours. The whole polymerization process keeps the reaction temperature at 80-82 ℃, after the dripping is finished, the temperature is kept for 0.5h, after the dripping is cooled to 50 ℃, ammonia water is used for adjusting the pH value of the emulsion to 7.0-8.0, and the styrene-acrylic emulsion with the glass transition temperature of 70 ℃ is obtained;
step 3, uniformly coating the styrene-acrylic emulsion on the surface of the FTO conductive glass by adopting a spin coating process, wherein spin coating parameters are 300rpm and 10s at a low speed; after repeated spin coating at a high speed 3000rpm for 20 seconds, the emulsion coated FTO glass was dried in an oven at 70 ℃ for use, referred to as a polymer modified FTO electrode.
Test examples
The products prepared in the above examples and comparative examples were tested and the results were as follows:
fig. 1 is a scanning electron microscope image of a polyaniline film prepared in example 1, fig. 2 is a scanning electron microscope image of a polymer modified electrode prepared in example 1, it can be seen that an emulsion film formed by coating styrene-acrylic emulsion on the electrode has uniform microscopic cracks, fig. 3 is a scanning electron microscope image of a film sample formed after electrodeposition in example 1, it can be seen that polyaniline grows well and deposits on the cracks, and it can be seen from fig. 1 that the whole structure of the prepared polyaniline film is loose and no obvious agglomeration phenomenon occurs;
FIG. 4 is a scanning electron microscope image of the polyaniline film prepared in comparative example 1, and it can be seen from the comparison of FIG. 1 and FIG. 4 that by introducing the styrene-acrylic emulsion template, the microscopic morphology of the polyaniline film material is improved, the size of the nanostructure is reduced, the morphology is more uniform, and the porosity is improved;
FIG. 5 is a scanning electron microscope image of a polyaniline film prepared in comparative example 2. As can be seen from the comparison of FIG. 5 and FIG. 1, by controlling the electrodeposition process of the polyaniline film material on the styrene-acrylic emulsion template, the polyaniline prepared in FIG. 1 by combining cyclic voltammetry and constant voltage deposition technique is in loose nanowire shape, and a plurality of nanoparticles are attached to the surface of the nanowire, which is beneficial to improving electrochemical active sites; whereas the polyaniline film prepared by cyclic voltammetry in fig. 5 only shows a simple nanowire structure;
FIG. 6 is a scanning electron microscope image of the polyaniline film prepared in example 2, similar to FIG. 1, the polyaniline film prepared by combining cyclic voltammetry and constant current deposition techniques also exhibits a loose micro-nano hierarchical structure;
FIG. 7 is a scanning electron microscope image of the polymer modified FTO electrode obtained in comparative example 3, and it can be seen from FIG. 7 that when the glass transition temperature of the styrene-acrylic emulsion reached 70 ℃, the latex particles could not form a film, thus failing to obtain an electrode with uniform micro cracks;
FIG. 8 is an optical photograph of the polyaniline film obtained in example 1 under different voltages, and it can be seen from FIG. 8 that the polyaniline electrochromic film based on the styrene-acrylic emulsion template structure according to the present invention can realize multi-color optical control characteristics;
FIG. 9 is a graph showing the transmittance of the polyaniline film obtained in example 1 at different voltages, and it can be seen from FIG. 9 that the polyaniline film has a large optical modulation capability between-0.2 and 1V voltage range, and the transmittance spectrum significantly changes with voltage;
FIG. 10 shows constant current charge and discharge curves of the polyaniline film obtained in example 1 under different current densities in a voltage range of-0.2 to 0.8V, wherein the charge and discharge curves are symmetrical, indicating that the material has good pseudocapacitance characteristics;
FIG. 11 is a graph showing the area specific capacity versus current density calculated from constant current charge-discharge curves of the polyaniline films obtained in example 1 and comparative example 1 over a voltage range of-0.2 to 0.8V, and the polyaniline film material prepared based on the styrene-acrylic emulsion template has better energy storage characteristics.
The invention uses the styrene-acrylic emulsion film electrode as a template, and adjusts the nucleation and growth positions of polyaniline on the electrode by regulating and controlling microscopic cracks of the styrene-acrylic emulsion film, thereby obtaining a micro-nano hierarchical structure with high porosity, being beneficial to ion injection and extraction, slowing down structural stress generated by electrochemical reaction, improving electrochemical reaction stability, and solving the problems of obvious attenuation of the color changing capability and poor circulation stability of polyaniline after the polyaniline undergoes multiple electrochemical circulation; meanwhile, a micro-nano hierarchical structure modified by nano particles is obtained on the loose polyaniline material by adopting a method of combining a cyclic voltammetry and a constant potential deposition method or combining the cyclic voltammetry and the constant current deposition method in the electrodeposition process, so that active sites of electrochemical reaction are increased, and the response speed is improved.
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, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. The preparation method of the polyaniline film with the micro-nano hierarchical structure based on the styrene-acrylic emulsion template is characterized by comprising the following steps of:
s1, preparing styrene-acrylic emulsion with a certain glass transition temperature; s2, coating the styrene-acrylic emulsion on a conductive substrate to form an emulsion film, drying under certain conditions,
obtaining a modified electrode with micro cracks;
s3, performing electrodeposition on the modified electrode to obtain a sample, and performing emulsion template removal treatment on the sample to obtain a polyaniline film;
in the step S1, the glass transition temperature of the styrene-acrylic emulsion is 40-60 ℃;
in the step S1, monomers used for preparing the styrene-acrylic emulsion are acrylic acid, hydroxypropyl methacrylate, methyl methacrylate, butyl acrylate and styrene;
in the step S3, the electrodeposition liquid is a mixed solution of hydrochloric acid or sulfuric acid, aniline and deionized water; in step S3, the cyclic voltammetry and potentiostatic deposition are combined or circulated in the electrodeposition process
A combination of voltammetry and galvanostatic deposition.
2. The method for preparing the polyaniline film with the micro-nano hierarchical structure based on the styrene-acrylic emulsion template according to claim 1, which is characterized in that: in step S2, spin coating is performed on the conductive substrate, and the obtained emulsion film is dried at a drying temperature of 70 ℃ after repeated coating.
3. The method for preparing the polyaniline film with the micro-nano hierarchical structure based on the styrene-acrylic emulsion template according to claim 1, which is characterized in that: the conductive substrate is one of ITO glass, FTO glass or conductive PET.
4. The method for preparing the polyaniline film with the micro-nano hierarchical structure based on the styrene-acrylic emulsion template according to claim 1, which is characterized in that: in the step S3, a three-electrode system is adopted for electrodeposition, the modified electrode in the step S2 is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode.
5. The thin polyaniline film with micro-nano hierarchical structure based on styrene-acrylic emulsion template according to claim 1
The preparation method of the film is characterized in that: in the step S3, the emulsion template removing treatment process comprises the following steps: the sample was washed with ethanol and soaked in a mixed solution of N, N-dimethylformamide and toluene for 12 hours, the mixed solution being replaced every 4 hours, the volume ratio of N, N-dimethylformamide to toluene being 1:1.
6. Polyaniline film with micro-nano hierarchical structure based on styrene-acrylic emulsion template, its characterized in that: the polyaniline film with the micro-nano hierarchical structure based on the styrene-acrylic emulsion template is prepared by the preparation method of the polyaniline film with the micro-nano hierarchical structure based on the styrene-acrylic emulsion template, and is a multi-color electrochromic energy storage material.
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