CN112608471A - High-crystallization-quality polypyrrole conductive film and preparation method thereof - Google Patents

High-crystallization-quality polypyrrole conductive film and preparation method thereof Download PDF

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CN112608471A
CN112608471A CN202011452642.7A CN202011452642A CN112608471A CN 112608471 A CN112608471 A CN 112608471A CN 202011452642 A CN202011452642 A CN 202011452642A CN 112608471 A CN112608471 A CN 112608471A
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film
polypyrrole
oxidant
polypyrrole conductive
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CN112608471B (en
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李炳生
卞万朋
王月飞
马剑钢
刘益春
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Northeast Normal University
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
    • C—CHEMISTRY; METALLURGY
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Abstract

The invention relates to a polypyrrole conductive film with high crystallization quality and a preparation method thereof, and the preparation method comprises the following steps: step 1, preparing a protonic acid solution, wherein deionized water is used as a solvent; step 2, weighing an oxidant, dissolving the oxidant in the acid solution, and fully stirring to completely dissolve the oxidant; step 3, taking pyrrole monomer and dripping into the solution, gradually observing that a polypyrrole film is formed on the liquid surface, wherein the film is more obvious along with the increase of polymerization time, and carrying out the reaction at constant temperature; step 4, fishing out the film generated in the step 3 from the liquid level by using a clean substrate, and cleaning the film by using deionized water to remove the reaction solution residue on the surface of the film; and 5, drying the film obtained in the step 4 to obtain the polypyrrole film with high crystallization quality.

Description

High-crystallization-quality polypyrrole conductive film and preparation method thereof
Technical Field
The invention relates to a preparation method of a conductive polypyrrole film, in particular to a high-quality conductive polypyrrole film prepared on a liquid surface by a chemical oxidation method and a preparation method thereof.
Background
The conductive polymer belongs to a conductive polymer material, polypyrrole is one of common conductive polymers, and the polypyrrole has the advantages of light weight, easy processing, good mechanical property, low cost and the like of the traditional polymer material, and also has the advantage of continuously adjustable conductivity by changing preparation conditions, so that the application range of the polypyrrole is greatly expanded.
Polyazoles are obtained by oxidative polymerization of pyrrole monomers, and there are generally two methods for their preparation: chemical oxidation and electrochemical oxidation.
The polypyrrole prepared by the method is usually powder, and no obvious diffraction peak is generated by X-ray diffraction. The electrochemical oxidation method can prepare the polypyrrole film, but needs to be on a fixed substrate, and is difficult to effectively peel and transfer.
Disclosure of Invention
The invention designs a high-crystallization-quality polypyrrole conductive film and a preparation method thereof, and solves the technical problems of respective defects of a chemical oxidation method and an electrochemical oxidation method for preparing the high-quality polypyrrole conductive film.
In order to solve the technical problems, the invention adopts the following scheme:
a preparation method of a polypyrrole conductive film with high crystallization quality comprises the following steps: step 1, preparing a protonic acid solution, wherein deionized water is used as a solvent; step 2, weighing an oxidant, dissolving the oxidant in the acid solution, and fully stirring to completely dissolve the oxidant; step 3, taking pyrrole monomer and dripping into the solution, gradually observing that a polypyrrole film is formed on the liquid surface, wherein the film is more obvious along with the increase of polymerization time, and carrying out the reaction at constant temperature; step 4, fishing out the film generated in the step 3 from the liquid level by using a clean substrate, and cleaning the film by using deionized water to remove the reaction solution residue on the surface of the film; and 5, drying the film obtained in the step 4 to obtain the polypyrrole film with high crystallization quality.
Preferably, the protonic acid in step 1 is hydrochloric acid, sulfuric acid, perchloric acid, dodecylbenzenesulfonic acid or camphorsulfonic acid.
Preferably, the pH value of the protonic acid solution in step 1 is in the range of 0.5 to 3.
Preferably, the oxidant in step 2 is ammonium persulfate, potassium permanganate, hydrogen peroxide or ferric chloride.
Preferably, the concentration of the oxidizing agent in the solution in step 2 is in the range of 0.01 to 0.1 mol/L.
Preferably, the growth rate and the oxidation degree of the thin film are adjusted in step 3 by a controlled variable method, i.e., the amount of pyrrole monomer is first determined, and then the concentration of the oxidant is changed, and the volume of the pyrrole monomer is between 0 and 10 muL.
Preferably, the reaction time in step 3 is in the range of 1 to 60 min.
Preferably, the reaction temperature is selected in the range of 0-60 ℃ in step 3.
Preferably, the substrate in step 4 is glass, silicon wafer, mica or polyimide.
A polypyrrole conductive film with high crystallization quality is characterized in that: prepared using the preparation method described above.
An electrode, characterized by: the material of the polypyrrole conductive thin film comprises the polypyrrole conductive thin film with high crystallization quality.
Compared with the prior art, the polypyrrole conductive thin film with high crystallization quality and the preparation method thereof have the following beneficial effects:
(1) the invention uses chemical oxidation method, without solid base, it polymerizes to form film on the liquid surface, the generated film floats on the liquid surface, and the needed solid base can be used to fish out the film conveniently.
(2) The growth speed and the oxidation degree of the film can be adjusted by adjusting the amount of pyrrole monomer and the concentration of oxidant, and the doping degree of the polypyrrole film can be adjusted by changing the concentration of protonic acid.
(3) The polypyrrole film prepared by the method has high crystallization quality, high degree of molecular chain order and good electrical property.
(4) The invention can prepare the polypyrrole film in a large area, and is convenient for transfer cutting.
Drawings
Fig. 1 is an XRD pattern of the high crystalline quality polypyrrole conductive thin film of the present invention.
FIG. 2 is a SEM picture of the high crystalline quality polypyrrole conductive film of the invention.
FIG. 3 shows a Raman spectrum of the polypyrrole conductive thin film of high crystalline quality according to the invention.
FIG. 4 is a IV diagram of a high crystalline quality polypyrrole conductive film of this invention.
Detailed Description
The present invention will be further described with reference to specific examples in order to better understand the present invention.
Example 1:
a preparation method of a polypyrrole film comprises the following steps:
step 1, measuring 99mL of deionized water by using a measuring cylinder, pouring the deionized water into a beaker, measuring 833 mu L of concentrated hydrochloric acid solution with the concentration of 12mol/L by using a pipette gun, adding the concentrated hydrochloric acid solution into the deionized water, and preparing hydrochloric acid aqueous solution with the pH = 1.
And 2, weighing 0.228 g of ammonium persulfate solid, dissolving the ammonium persulfate solid in the prepared dilute hydrochloric acid solution, and stirring to fully dissolve the ammonium persulfate solid, wherein the concentration of the ammonium persulfate is 0.01 mol/L.
And 3, pouring the mixed solution into a glass culture dish, putting the glass culture dish into a refrigerator for refrigeration, keeping the temperature at 0 ℃, taking 5 mu L of pyrrole monomer to drop into the mixed solution after the temperature of the solution is reduced to 0 ℃, fishing out the polypyrrole film by using a clean 1X 1cm quartz glass substrate after 10 minutes, carefully washing the film by using deionized water to remove the residual mixed solution, putting the quartz glass substrate with the polypyrrole film into an oven for drying after the film is cleaned, and setting the temperature to be 60 ℃ for 30 minutes. Thus obtaining the polypyrrole film.
And (4) analyzing results:
FIG. 1 is a scanning electron microscope image of the prepared polypyrrole film, which shows that the continuity of the film is better and the surface is smoother. In order to determine the crystallization quality of the prepared film, the film is fished out by clean quartz glass, cleaned and dried, and then is subjected to an X-ray diffraction test.
Fig. 2 shows XRD test results. For clarity of illustration, the diffraction peaks of the substrate are given together here. Compared with the polypyrrole film prepared by the method disclosed by the invention, the polypyrrole film has two obvious diffraction peaks, the peak width is less than 1 degree, and the crystallization quality of the film is far superior to that of the film prepared by the prior art. The high crystallization quality indicates that the long chain of the polymer film has high order degree, and is more favorable for the transmission of current carriers.
Fig. 3 shows the distribution of raman shift of the polypyrrole film.
FIG. 4 is a current-voltage curve of a polypyrrole film, which shows that the film has better conductivity, and the carrier concentration and mobility tests are performed to further determine the electrical properties of the film, and the result shows that the carrier concentration is as high as 1021cm-3Mobility of 102cm2V-1s-1The conductive electrode can be used for preparing capacitors, microelectronic devices and the like.
Example 2:
step 1, measuring 99mL of deionized water, putting the deionized water into a beaker, measuring 27 mu L of concentrated sulfuric acid with the mass fraction of 98% by using a pipette, adding the concentrated sulfuric acid into the deionized water, and preparing a dilute sulfuric acid solution with the pH = 2.
And 2, weighing 1.622 g of ferric chloride solid, dissolving the ferric chloride solid in the prepared dilute sulfuric acid solution, and stirring to fully dissolve the ferric chloride solid, wherein the concentration of the obtained ferric chloride is 0.1 mol/L.
And 3, pouring the mixed solution into a glass culture dish, dripping 20 mu L of pyrrole monomer into the mixed solution at the room temperature of 25 ℃, fishing out the polypyrrole film by using a clean 1X 1cm quartz glass substrate after 2 minutes, carefully washing the film by using deionized water to remove the residual mixed solution, putting the quartz glass substrate with the polypyrrole film into an oven to be dried after the washing is finished, setting the temperature to be 60 ℃, and keeping the time for 30 minutes to obtain the polypyrrole film.
The polypyrrole film prepared by the method has high crystallization quality and good conductivity, does not need a substrate, and can be used as an electrode for preparing a microelectronic device.
The invention is described above with reference to the accompanying drawings, it is obvious that the implementation of the invention is not limited in the above manner, and it is within the scope of the invention to adopt various modifications of the inventive method concept and solution, or to apply the inventive concept and solution directly to other applications without modification.

Claims (10)

1. A preparation method of a polypyrrole conductive film with high crystallization quality comprises the following steps:
step 1, preparing a protonic acid solution, wherein deionized water is used as a solvent;
step 2, weighing an oxidant, dissolving the oxidant in the acid solution, and fully stirring to completely dissolve the oxidant;
step 3, taking pyrrole monomer and dripping into the solution, gradually observing that a polypyrrole film is formed on the liquid surface, wherein the film is more obvious along with the increase of polymerization time, and carrying out the reaction at constant temperature;
step 4, fishing out the film generated in the step 3 from the liquid level by using a clean substrate, and cleaning the film by using deionized water to remove the reaction solution residue on the surface of the film;
and 5, drying the film obtained in the step 4 to obtain the polypyrrole film with high crystallization quality.
2. The method for preparing a polypyrrole conductive film with high crystalline quality according to claim 1, wherein: in the step 1, the protonic acid is hydrochloric acid, sulfuric acid, perchloric acid, dodecyl benzene sulfonic acid or camphor sulfonic acid.
3. The method for preparing a polypyrrole conductive film with high crystalline quality according to claim 1, wherein: the pH value range of the protonic acid solution in the step 1 is 0.5-3.
4. The method for preparing a polypyrrole conductive film with high crystalline quality according to claim 1, wherein: and in the step 2, the oxidant is ammonium persulfate, potassium permanganate, hydrogen peroxide or ferric trichloride.
5. The method for preparing a polypyrrole conductive film with high crystalline quality according to claim 1, wherein: the concentration range of the oxidant in the solution in the step 2 is 0.01-0.1 mol/L.
6. The method for preparing a polypyrrole conductive film with high crystalline quality according to claim 1, wherein: in the step 3, the growth speed and the oxidation degree of the film are adjusted by controlling a variable method, namely firstly determining the amount of pyrrole monomer, and then changing the concentration of an oxidant, wherein the volume of the pyrrole monomer is between 0 and 10 mu L.
7. The method for producing a high crystalline quality polypyrrole conductive thin film according to any one of claims 1 to 6, wherein: the reaction time range in the step 3 is 1-60 min; alternatively/or additionally, the reaction temperature in step 3 is selected in the range of 0 to 60 ℃.
8. The method for producing a high crystalline quality polypyrrole conductive thin film according to any one of claims 1 to 7, wherein: in the step 4, the substrate is glass, silicon chip, mica or polyimide.
9. A polypyrrole conductive film with high crystallization quality is characterized in that: prepared using the preparation process according to any one of claims 1 to 8.
10. An electrode, characterized by: the material of the polypyrrole conductive thin film comprises the high-crystalline-quality polypyrrole conductive thin film in the claim 9.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516538A (en) * 2011-12-15 2012-06-27 河海大学 Method for preparing fibrillar meshwork structure conducting polypyrrole film by interfacial polymerization
CN102899898A (en) * 2012-10-31 2013-01-30 东华大学 Method for preparing flexible conductive polypyrrole compound fabric for flexible electrode of supercapacitor
CN102923747A (en) * 2012-11-28 2013-02-13 东北大学 Method for producing aluminum chloride, silicon chloride and ferric chloride by utilizing coal gangue
CN109161529A (en) * 2018-08-23 2019-01-08 长春理工大学 A kind of film of poly pyrrole substrate preparation method for cell culture
CN109786124A (en) * 2018-12-05 2019-05-21 南通科技职业学院 A kind of flexible asymmetric super-capacitor and preparation method thereof
CN112678779A (en) * 2021-02-02 2021-04-20 天津大学 Preparation method of ammonium persulfate crystal

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516538A (en) * 2011-12-15 2012-06-27 河海大学 Method for preparing fibrillar meshwork structure conducting polypyrrole film by interfacial polymerization
CN102899898A (en) * 2012-10-31 2013-01-30 东华大学 Method for preparing flexible conductive polypyrrole compound fabric for flexible electrode of supercapacitor
CN102923747A (en) * 2012-11-28 2013-02-13 东北大学 Method for producing aluminum chloride, silicon chloride and ferric chloride by utilizing coal gangue
CN109161529A (en) * 2018-08-23 2019-01-08 长春理工大学 A kind of film of poly pyrrole substrate preparation method for cell culture
CN109786124A (en) * 2018-12-05 2019-05-21 南通科技职业学院 A kind of flexible asymmetric super-capacitor and preparation method thereof
CN112678779A (en) * 2021-02-02 2021-04-20 天津大学 Preparation method of ammonium persulfate crystal

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
沙兆林等: "化学氧化法合成聚吡咯薄膜", 《化学研究与应用》 *

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