CN111223678A - Method for preparing PPy flexible capacitor film conductor with porous structure - Google Patents

Method for preparing PPy flexible capacitor film conductor with porous structure Download PDF

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CN111223678A
CN111223678A CN202010018593.XA CN202010018593A CN111223678A CN 111223678 A CN111223678 A CN 111223678A CN 202010018593 A CN202010018593 A CN 202010018593A CN 111223678 A CN111223678 A CN 111223678A
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diatomite
mixture
pyrrole
film
ppy
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樊凯
林雪山
苏江
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Chongqing College of Electronic Engineering
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses a method for preparing a PPy flexible capacitor film conductor with a porous structure, which comprises the following steps of 1) adding diatomite into pyrrole and uniformly mixing to prepare a first mixture consisting of the diatomite and the pyrrole; 2) uniformly coating the first mixture on a plane carrier, and forming a first mixture film of polypyrrole-coated diatomite on the plane carrier through polymerization reaction; 3) and etching the dried first mixture film on the planar carrier by using hydrofluoric acid, and removing the diatomite in the first mixture film to obtain the flexible supercapacitor conductor. According to the invention, a large number of uniformly arranged holes are distributed on the surface and inside of the diatomite, in the preparation process, pyrrole monomers enter the holes in the diatomite, PPy polymers are filled in the holes of the diatomite after polymerization reaction, and after a diatomite template is removed by etching, a large number of structures similar to the holes are formed on the PPy membrane, so that the specific surface area of the PPy membrane is greatly increased, and the charge storage capacity is greatly improved.

Description

Method for preparing PPy flexible capacitor film conductor with porous structure
Technical Field
The invention relates to the technical field of flexible capacitors, in particular to a preparation method of a flexible supercapacitor conductor.
Background
Polypyrrole (PPy) is a conductive polymer, which is polymerized from pyrrole monomers, and polypyrrole films can be used as conductors of flexible capacitors. However, the polypyrrole film prepared in the prior art has a low specific surface area and a weak capacity of storing electricity.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a flexible capacitor thin film conductor of PPy having a porous structure, so as to solve the technical problem that a polypyrrole thin film prepared in the prior art has a weak capacity of storing electricity.
The invention discloses a method for preparing a PPy flexible capacitor film conductor with a porous structure, which comprises the following steps:
1) adding diatomite into pyrrole and uniformly mixing to prepare a first mixture consisting of diatomite and pyrrole; or adding diatomite and carbon nanotube into pyrrole, and mixing to obtain a second mixture composed of diatomite, carbon nanotube and pyrrole;
2) uniformly coating the first mixture on a plane carrier, and forming a first mixture film of polypyrrole-coated diatomite on the plane carrier through polymerization reaction; or uniformly coating the second mixture on a planar carrier, and forming a second mixture film of polypyrrole-coated diatomite and carbon nanotubes on the planar carrier through polymerization reaction;
3) etching the dried first mixture film on the planar carrier by using hydrofluoric acid, and removing diatomite in the first mixture film to obtain a flexible supercapacitor conductor;
or etching the second mixture film dried on the planar carrier by using hydrofluoric acid to remove the diatomite in the second mixture film, thereby obtaining the flexible supercapacitor conductor.
Further, the mass ratio of the diatomite to the pyrrole in the first mixture is as follows: 0.01: 10-0.1: 10;
the mass ratio of the diatomite, the carbon nano-tubes and the pyrrole in the second mixture is as follows: 0.01: 0.05: 10-0.1: 0.05: 10.
further, in step 1), the diatomaceous earth and the pyrrole are uniformly mixed by ultrasonic oscillation, and the diatomaceous earth, the carbon nanotubes and the pyrrole are uniformly mixed by ultrasonic oscillation.
Further, the mass concentration of the hydrofluoric acid is as follows: 40 to 20 percent.
The invention has the beneficial effects that:
1. the invention relates to a method for preparing a PPy flexible capacitor film conductor with a porous structure, which adopts diatomite with a large number of uniformly arranged holes distributed on the surface and inside, wherein pyrrole monomers enter the holes in the diatomite in the preparation process, PPy polymers are filled in the holes of the diatomite after polymerization reaction, and a large number of structures similar to the holes are formed on a PPy film after a diatomite template is removed by etching, so that the specific surface area of the PPy film is greatly increased, and the capacity of storing charges is also greatly improved.
2. According to the method for preparing the PPy flexible capacitor film conductor with the porous structure, the specific surface area of the PPy flexible capacitor film conductor is further improved and the charge storage capacity is further enhanced by adding the carbon nanotube structure in the Ppy film.
Drawings
Fig. 1 is a schematic flow chart of a process for preparing a PPy flexible capacitor thin film conductor with a porous structure.
Fig. 2 is a microscopic morphology of the original diatomaceous earth particles observed by SEM.
Fig. 3 is a microscopic morphology of the diatomaceous earth surface coated with PPy observed by SEM.
Fig. 4 is the microstructure of the PPy film after HF acid etching of the diatomaceous earth observed by SEM.
FIG. 5 is a surface structure of a Ppy, diatomaceous earth, and carbon nanotube mixture film etched by HF acid observed by SEM.
Fig. 6 is a sectional thickness view of the PPy flexible capacitor thin-film conductor observed by SEM.
Fig. 7 is a microstructure view of a thin film conductor of a PPy flexible capacitor before and after etching, observed by TEM.
Fig. 8 is a surface structure view of an original PPY film observed by AFM.
Fig. 9 is a surface structure view of the PPY film after the addition of diatomaceous earth, which was observed by AFM.
Fig. 10 is a surface structure view of the PPy film after etching diatomaceous earth with HF acid, which was observed by AFM.
FIG. 11 is a surface structure view of a Ppy, diatomaceous earth and carbon nanotube mixture thin film etched by HF acid, which was observed by AFM.
Detailed Description
The invention is further described below with reference to the figures and examples.
The first embodiment is as follows: the method for preparing the thin film conductor of the PPy flexible capacitor with the porous structure comprises the following steps:
1) adding diatomite into pyrrole, and uniformly mixing by ultrasonic oscillation to prepare a first mixture consisting of the diatomite and the pyrrole. In this example, the mass ratio of diatomaceous earth to pyrrole is: 0.01: 10.
2) uniformly coating the first mixture on a plane carrier, and forming a first mixture film of polypyrrole-coated diatomite on the plane carrier through polymerization reaction; the planar support in this example is filter paper.
The polymerization equation for pyrrole is as follows:
Figure BDA0002359865080000031
3) and etching the dried first mixture film on the planar carrier by using hydrofluoric acid, and removing the diatomite in the first mixture film to obtain the flexible supercapacitor conductor. The mass concentration of the hydrofluoric acid is as follows: 20 percent.
The reaction equation for etching diatomaceous earth is as follows:
SiO2+4HF＝SiF4↑+2H2O
example two: the method for preparing the thin film conductor of the PPy flexible capacitor with the porous structure comprises the following steps:
1) adding diatomite into pyrrole, and uniformly mixing by ultrasonic oscillation to prepare a first mixture consisting of the diatomite and the pyrrole. In this example, the mass ratio of diatomaceous earth to pyrrole is: 0.05: 10.
2) uniformly coating the first mixture on a plane carrier, and forming a first mixture film of polypyrrole-coated diatomite on the plane carrier through polymerization reaction; the planar support in this example is filter paper.
3) And etching the dried first mixture film on the planar carrier by using hydrofluoric acid, and removing the diatomite in the first mixture film to obtain the flexible supercapacitor conductor. In this example, the mass concentration of hydrofluoric acid was 30%.
Example three: the method for preparing the thin film conductor of the PPy flexible capacitor with the porous structure comprises the following steps:
1) adding diatomite into pyrrole, and uniformly mixing by ultrasonic oscillation to prepare a first mixture consisting of the diatomite and the pyrrole. In this example, the mass ratio of diatomaceous earth to pyrrole is: 0.1: 10.
2) uniformly coating the first mixture on a plane carrier, and forming a first mixture film of polypyrrole-coated diatomite on the plane carrier through polymerization reaction. The planar support in this example is filter paper.
3) And etching the dried first mixture film on the planar carrier by using hydrofluoric acid, and removing the diatomite in the first mixture film to obtain the flexible supercapacitor conductor. In this embodiment, the mass concentration of hydrofluoric acid is: 40 percent.
Example four: the method for preparing the thin film conductor of the PPy flexible capacitor with the porous structure comprises the following steps:
1) adding diatomite and the carbon nano-tubes into pyrrole, and uniformly mixing by ultrasonic oscillation to prepare a second mixture consisting of the diatomite, the carbon nano-tubes and the pyrrole. In this example, the mass ratio of the diatomaceous earth, the carbon nanotubes, and the pyrrole is: 0.01: 0.05: 10.
2) uniformly coating the second mixture on a planar carrier, and forming a second mixture film of polypyrrole-coated diatomite and carbon nanotubes on the planar carrier through polymerization reaction; the planar support in this example is filter paper. The polymerization equation for pyrrole is as follows:
Figure BDA0002359865080000051
3) etching the second mixture film dried on the planar carrier by using hydrofluoric acid to remove the diatomite in the second mixture film to obtain a flexible supercapacitor conductor; the mass concentration of hydrofluoric acid in this example is: 20 percent.
The reaction equation for etching diatomaceous earth is as follows:
SiO2+4HF＝SiF4↑+2H2O
example five: the method for preparing the thin film conductor of the PPy flexible capacitor with the porous structure comprises the following steps:
1) adding diatomite and the carbon nano-tubes into pyrrole, and uniformly mixing by ultrasonic oscillation to prepare a second mixture consisting of the diatomite, the carbon nano-tubes and the pyrrole. In this example, the mass ratio of the diatomaceous earth, the carbon nanotubes, and the pyrrole is: 0.05: 0.05: 10.
2) uniformly coating the second mixture on a planar carrier, and forming a second mixture film of polypyrrole-coated diatomite and carbon nanotubes on the planar carrier through polymerization reaction; the planar support in this example is filter paper.
3) Etching the second mixture film dried on the planar carrier by using hydrofluoric acid to remove the diatomite in the second mixture film to obtain a flexible supercapacitor conductor; the mass concentration of hydrofluoric acid in this example is: 30 percent.
Example six: the method for preparing the thin film conductor of the PPy flexible capacitor with the porous structure comprises the following steps:
1) adding diatomite and the carbon nano-tubes into pyrrole, and uniformly mixing by ultrasonic oscillation to prepare a second mixture consisting of the diatomite, the carbon nano-tubes and the pyrrole. In this example, the mass ratio of the diatomaceous earth, the carbon nanotubes, and the pyrrole is: 0.1:0.05: 10.
2) uniformly coating the second mixture on a planar carrier, and forming a second mixture film of polypyrrole-coated diatomite and carbon nanotubes on the planar carrier through polymerization reaction; the planar support in this example is filter paper.
3) Etching the second mixture film dried on the planar carrier by using hydrofluoric acid to remove the diatomite in the second mixture film to obtain a flexible supercapacitor conductor; the mass concentration of the hydrofluoric acid is as follows: 40 percent.
Fig. 2 to 6 are views for observing the influence of the method of etching diatomaceous earth on the internal structure of a material by an electron scanning microscope (SEM). Fig. 2 is a micro-morphology of original diatomite particles, and it can be seen from the figure that the surface of the diatomite particles has uniform pore distribution, which provides a good template for preparing a PPy flexible electrode membrane material with a specific microstructure. Fig. 3 is a microscopic morphology of the diatomite surface coated with PPy, and it can be seen from the figure that the PPy formed after polymerization can effectively and completely cover diatomite particles, and the surface of the covered material still presents a specific ordered structure of diatomite, which illustrates that the method can realize uniformity of coverage. Fig. 4 is a microstructure after HF acid etching, and it can be seen that after the etching reaction, the diatomite particles are completely removed, and the PPy still maintains the microstructure before the reaction, which illustrates that this etching method based on diatomite as a template is an effective method for preparing PPy electrode membrane material with special microstructure.
FIG. 5 shows the surface structure of a Ppy, diatomite and carbon nanotube mixture film after HF acid etching, and it can be seen from the figure that after the diatomite particles are etched, a pore-like structure is formed on the film surface, and after the pore structure is partially enlarged, as shown in the enlarged part at the upper right corner in FIG. 5, the structure that the carbon nanotubes are added to form bridges between the walls of the pores can be seen.
The addition of diatomaceous earth also has some effect on the thickness of the produced PPy membrane material. As shown in FIG. 6, FIG. 6(a) is a cross-sectional structure of a membrane material without adding diatomaceous earth, and the average thickness thereof is about 3.1 mm. FIG. 6(b) shows a cross-sectional structure of the membrane after addition of the diatomaceous earth particles, the thickness of which has increased to about 4.3 mm. The results show that the thickness of the film is increased to a certain extent after the diatomite is added, and further provides a basis for increasing the charge storage capacity of the material.
As shown in fig. 7, the influence of the etched diatomaceous earth on the internal structure of the material was observed by a Transmission Electron Microscope (TEM). Since PPy is amorphous and effectively coats diatomaceous earth, the prepared PPy and diatomaceous earth mixture thin film has no microscopically obvious ordered structure before etching, as shown in fig. 7 (a). On the contrary, due to the ordered pore structure on the surface of the diatomite, in the process of preparing the membrane, the monomer penetrates into the pores through the ultrasonic action, and the PPy polymer formed after the polymerization reaction is effectively fixed in the pores after vacuum drying. After the etching reaction, the diatomaceous earth template was removed and the polymer filled in the pores remained, and in a partial region of the film surface, a micro-ordered structure with nonuniform orientation was formed, as shown in fig. 7 (b). Meanwhile, the generation of diffraction rings can be seen on the electron diffraction diagram of a transmission electron microscope, which also indicates that an ordered structure is generated after the surface of the microscopic film material is etched, as shown in fig. 7 (c).
Fig. 8 to 11 are views for observing the influence of etching diatomaceous earth on the internal structure of the material by Atomic Force Microscopy (AFM). FIG. 8 is a raw PPY film, from which it can be seen that the film surface roughness is relatively low. When diatomaceous earth was added, as shown in fig. 9, the surface roughness of the film was increased, and more protrusions and depressions appeared, corresponding to the influence of the pore structure of the diatomaceous earth particles on the surface roughness of the film. After the diatomite is etched, the surface roughness of the film is increased compared with the prior art, as shown in fig. 10, which shows that the surface of the etched film material has uniform concave height distribution, and the etching method based on the diatomite as the template can effectively improve the specific surface area of the film, and provides conditions for loading more charges and preparing high-performance electrode materials. In addition, with the addition of the improved structure of the carbon nanotubes, as shown in fig. 1, it can be seen that the roughness of the surface of the film material is further increased due to the special morphological characteristics of the carbon nanotubes, which also indicates that the addition of the carbon nanotubes can effectively improve the specific surface area of the film, and is also a method for effectively improving the performance of the electrode material.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (4)

1. A method for preparing a PPy flexible capacitor film conductor with a porous structure is characterized in that: the method comprises the following steps:
1) adding diatomite into pyrrole and uniformly mixing to prepare a first mixture consisting of diatomite and pyrrole; or adding diatomite and carbon nanotube into pyrrole, and mixing to obtain a second mixture composed of diatomite, carbon nanotube and pyrrole;
2) uniformly coating the first mixture on a plane carrier, and forming a first mixture film of polypyrrole-coated diatomite on the plane carrier through polymerization reaction; or uniformly coating the second mixture on a planar carrier, and forming a second mixture film of polypyrrole-coated diatomite and carbon nanotubes on the planar carrier through polymerization reaction;
3) etching the dried first mixture film on the planar carrier by using hydrofluoric acid, and removing diatomite in the first mixture film to obtain a flexible supercapacitor conductor;
or etching the second mixture film dried on the planar carrier by using hydrofluoric acid to remove the diatomite in the second mixture film, thereby obtaining the flexible supercapacitor conductor.
2. The method of preparing a PPy flexible capacitor film conductor with porous structure of claim 1, wherein: the mass ratio of the diatomite to the pyrrole in the first mixture is as follows: 0.01: 10-0.1: 10;
the mass ratio of the diatomite, the carbon nano-tubes and the pyrrole in the second mixture is as follows: 0.01: 0.05: 10-0.1: 0.05: 10.
3. the method of preparing a PPy flexible capacitor film conductor with porous structure of claim 1, wherein: in the step 1), the diatomite and the pyrrole are uniformly mixed by ultrasonic oscillation, and the diatomite, the carbon nanotube and the pyrrole are uniformly mixed by ultrasonic oscillation.
4. The method of preparing a PPy flexible capacitor film conductor with porous structure of claim 1, wherein: the mass concentration of the hydrofluoric acid is as follows: 40 to 20 percent.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1786036A (en) * 2004-12-08 2006-06-14 北京大学 Polymer/carbon mano-tube composite film and its preparation method
CN1995132A (en) * 2006-12-26 2007-07-11 西安交通大学 Preparation method of conductive high polymer and carbon nanotube composite electrode material
CN101093750A (en) * 2007-07-13 2007-12-26 厦门大学 Method for modifying surface of aluminum electrode foil
US20120182666A1 (en) * 2009-11-17 2012-07-19 Lumimove, Inc. D/B/A Crosslink Conductive polymer composites
CN102517638A (en) * 2011-11-17 2012-06-27 东南大学 Polypyrrole ordered nanopore array material as well as preparation method and energy storage application thereof
CN102660754A (en) * 2012-05-16 2012-09-12 上海大学 Preparation method of polypyrrole carbon nanotube composite with high specific capacitance
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CN103112238A (en) * 2013-01-28 2013-05-22 电子科技大学 Preparation method of conducting polymer composite thin film
CN104392844A (en) * 2014-11-06 2015-03-04 东华大学 In-situ interfacial polymerization method of fiber-based conductive polypyrrole/carbon nano tube composite electrode material
CN105161316A (en) * 2015-09-16 2015-12-16 中国科学院电工研究所 Flexible super capacitor and preparation method thereof
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CN106206057A (en) * 2016-08-04 2016-12-07 北京极豆科技有限公司 A kind of Asymmetric Supercapacitor and preparation method thereof
CN108384045A (en) * 2018-03-06 2018-08-10 常州大学 The method that graphene-supported modified polyaniline prepares superelevation specific capacitance nanocomposite

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Application publication date: 20200602