KR101153746B1 - Method of Manufacturing conductive polyaniline/actMethod of Manufacturing conductive polyaniline/activate carbon composites for electrode material of ivate carbon composites for electrode material of capacitor capacitor - Google Patents
Method of Manufacturing conductive polyaniline/actMethod of Manufacturing conductive polyaniline/activate carbon composites for electrode material of ivate carbon composites for electrode material of capacitor capacitor Download PDFInfo
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- 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
Abstract
The present invention comprises the steps of adding activated carbon to the acid solution and stirring to form an activated carbon dispersion solution; Adding and dispersing aniline monomer in the dispersion solution, and adding a polymerization initiator having the same molar concentration; And a method of preparing a polyaniline / activated carbon composite material, a polyaniline / activated carbon composite material, comprising: synthesizing polyaniline on a surface of the activated carbon by a polymerization reaction. According to the present invention, the synthesis and doping of the polyaniline and the coating process on the surface of the activated carbon occur at one time, thereby shortening the synthesis time of the composite material, and obtaining a larger capacitance than when using the activated carbon alone or using the polyaniline alone, and the capacitor electrode. When used as a capacitor, a capacitor electrode having better performance than a conventional capacitor can be obtained.
Description
The present invention relates to a method for producing a polyaniline / activated carbon composite material for a capacitor electrode material, and more particularly, to polyaniline for a capacitor electrode material capable of satisfying both a rechargeable battery and a conventional capacitor characteristic. It relates to a method for producing an activated carbon composite material.
Carbon materials, which are conventionally used as capacitor electrode materials, have structural stability but limited theoretical charge capacity. In order to achieve the high charge capacity required for supercapacitors, various alternative materials such as conductive polymers and metal oxides have been introduced.
Conjugation polymers have a higher capacity than carbon, have excellent mechanical, chemical and optical properties, and have the potential for corrosion stability, chemical or electrochemical synthesis. Such polymers are based on having single and double bonds between atoms, in particular between carbon and carbon atoms, and between carbon and nitrogen atoms. Compounds having such conjugated bonds do not show conductivity by themselves, but doping with a dopant shows conductivity.
Due to the above properties, conductive polymers are being used in various applications such as solar cells, lightweight batteries, light emitting diodes, energy storage devices, and sensors. Among the conductive polymers, polyaniline has attracted much attention due to its low price, environmental stability, and easy synthesis.
Polyaniline can be used as an electrical material because of its reversible proton doping, reproducibility of redox reactions, and electrical conductivity. However, the charging capacity is high, but the cycle life (cyclic life) is low, there is a big disadvantage in the volume change during charging and discharging. In order to solve this problem, research on a composite material of carbon material and polyaniline has been conducted.
As a method for synthesizing polyaniline, MacDiarmid et al. Proposed a process for synthesizing aniline monomers with polyaniline under an aqueous hydrochloric acid solution, dedoping with a base solution, and re-doping with various acids (AG MacDiarmid et. Al., Synthetic Metals, 18 (1987). ), p285-290). Since then, various methods have been proposed, such as synthesizing polyaniline into a film using an electrochemical polymerization method, synthesizing polyaniline into powder by chemical oxidation, using an organic solvent, or using two or three dopants together. .
Since then, polyaniline has been widely used throughout the industry, and research on making composites with other materials, such as coating metal with polyaniline to prevent oxidation or using it as a support for a catalyst, has been continued for a long time.
The work of synthesizing composites of polyaniline and carbon materials began in the mid-2000s, beginning around 1990 (B. Zingera et. Al., "Electrocoating of carbon fibers with polyaniline and poly (hydroxyalkyl methacrylates)," 1989). Is going on.
When polyaniline is coated on the surface of activated carbon, new covalent bonds are created between the carbon of activated carbon and the carbon of the polyaniline main chain or the nitrogen of the polybenzene's outer benzene ring (Huseyin Zengin et. Al., Materials Chemistry and Physics 120 (2010), p 50).
There are a variety of methods for synthesizing composite materials of polyaniline / carbon materials. Method of dissolving pre-synthesized polyaniline in a solvent and coating on carbon material, method of coating pre-synthesized polyaniline on carbon material by electrochemical method, adsorbing aniline monomer on surface of carbon material and proceeding polymerization And dispersing the carbon material in an acid solution in which aniline monomer is dissolved, and then making a film by an electrochemical method.
In the case of the method of dissolving the pre-synthesized polyaniline in a solvent and coating it on the carbon material, the process of synthesizing the polyaniline and filtering and drying the precipitate itself takes 24 hours or more. The problem is that it takes too long.
In addition, the polymerization reaction is carried out after the aniline monomer is adsorbed on the surface of the carbon material. In this case, since the aniline monomer is adsorbed on the surface of the carbon material and the polymerization process has to be performed separately, there is a problem that the formation of the composite material takes too long.
In addition, when a film is made of polyaniline and a carbon material by using an electrochemical method, since a film is formed on the used substrate, it is difficult to separate the composite material synthesized in the form of a film from the electrode, which makes it difficult to process and utilize the composite material. In addition, there is a problem in that there is a limit in the area of the electrode surface and the amount of activated carbon attached to the easy to produce a small amount, but there is a limit in producing a large amount of composite material.
In order to solve the above problems, the present invention provides a method for producing a polyaniline / activated carbon composite material in which the polyaniline is polymerized on the surface of the activated carbon in the presence of activated carbon and aniline monomers, and the surface coating and aniline polymerization proceed simultaneously. The purpose.
Another object of the present invention is to provide a polyaniline / activated carbon composite material formed by polymerizing polyaniline on the surface of activated carbon in the presence of activated carbon and aniline monomers.
In addition, an object of the present invention is to provide a capacitor electrode produced using the polyaniline / activated carbon composite material prepared by the above production method.
In order to achieve the above object, the present invention
Adding activated carbon to an acid solution and then stirring to form an activated carbon dispersion solution;
Adding and dispersing aniline monomer in the dispersion solution, and adding a polymerization initiator having the same molar concentration; And
It provides a method for producing a polyaniline / activated carbon composite material comprising a; polyaniline is synthesized on the surface of the activated carbon by a polymerization reaction.
In order to achieve the above another object, the present invention
Activated carbon was added to the acid solution, followed by stirring to disperse the activated carbon, and aniline monomer was added and dispersed in the solution.
A polymer polymerization initiator of the same molar concentration is added to provide a polyaniline / activated carbon composite material in which polyaniline is formed on the surface of the activated carbon.
In order to achieve the above another object, the present invention
Activated carbon was added to the acid solution, followed by stirring to disperse the activated carbon, and aniline monomer was added and dispersed in the solution, and the polymer polymerization initiator of the same molar concentration was added to form the polyaniline / activated carbon composite material in which polyaniline was formed on the surface of the activated carbon. Provide a capacitor electrode.
Synthesis method of the polyaniline / activated carbon composite material according to the present invention has the effect of shortening the synthesis time of the composite material because the polyaniline synthesis, doping process, coating process on the surface of the activated carbon occurs at once. Depending on the amount of activated carbon added during synthesis, polyaniline / activated carbon composite materials of various composition ratios can be synthesized.
The polyaniline / activated carbon composite material prepared according to the present invention has an additional capacity by the non-Faraday mechanism of activated carbon and by the Faraday mechanism by the oxidation / reduction reaction of polyaniline, which can be obtained when using conventional activated carbon alone or using polyaniline alone. A larger capacity than that can be obtained.
When the polyaniline / activated carbon composite material synthesized through the present invention is used as a capacitor electrode, a capacitor electrode having better performance than a conventional capacitor can be obtained.
1 illustrates a process of synthesizing polyaniline on a surface of activated carbon and a model of a polyaniline / activated carbon composite material according to an embodiment of the present invention.
2 is a graph showing the XRD analysis results of Examples 1,2 and 3 according to an embodiment of the present invention.
3 is a graph showing the results of XRD analysis of Comparative Examples 1,2 according to an embodiment of the present invention.
4 is a graph illustrating a cyclic voltage current measurement result of Examples 1, 2 and 3 according to an embodiment of the present invention.
5 is a graph illustrating a cyclic voltage current measurement result of Comparative Examples 1 and 2 according to one embodiment of the present invention.
Hereinafter, the present invention will be described in detail with reference to the drawings.
The present invention comprises the steps of adding activated carbon to the acid solution and stirring to form an activated carbon dispersion solution; Adding and dispersing aniline monomer in the dispersion solution, and adding a polymerization initiator having the same molar concentration; And a step of synthesizing the polyaniline on the surface of the activated carbon by a polymerization reaction.
The present invention is to make a polyaniline / carbon composite material through a polymer polymerization reaction in the presence of aniline monomer and carbon material together, the synthesis time is short, mass production is possible and the result is obtained in powder form for use in other fields It is easy.
Various carbon materials such as carbon sheets, carbon fibers, and carbon nanotubes may be used for the carbon material in the polyaniline / carbon material composite material. In the present invention, activated carbon is used as the carbon material to form a polyaniline / carbon material composite material for use as a capacitor electrode. If the use of polyaniline / carbon material composites is generalized, polyaniline / activated carbon composites will be the most widely used because activated carbon is a cheaper and more commonly used material than other carbon materials.
The polyaniline / activated carbon composite material has different filling capacities and electrochemical properties depending on the content of polyaniline and activated carbon constituting the material. When the amount of activated carbon is too large or the amount of polyaniline is too large, it is difficult to obtain the improved characteristics of the composite material by biasing one side of the characteristics. When the content of polyaniline and activated carbon is appropriate, it exhibits superior characteristics than conventional polyaniline and activated carbon. For this purpose, it is important to properly control the component ratio of the polyaniline / activated carbon composite material.
For example, the lower the amount of activated carbon in the composite material synthesis, the more polyaniline is produced on the surface of activated carbon, and the more activated carbon is, the wider the activated carbon surface area is throughout the reaction system, and the amount of aniline monomer present in the reaction system is limited. Therefore, the greater the amount of activated carbon, the less the amount of aniline monomer present per unit area. This leads to the same result even when the polymerization reaction occurs and the aniline monomer is synthesized into polyaniline.
Polyaniline / activated carbon composites will interact between polyaniline and activated carbon coated on the surface of activated carbon. When polyaniline is synthesized on the surface of activated carbon, there is an interaction between carbon of activated carbon and carbon of the main chain of polyaniline or nitrogen of the outer benzene ring of polyaniline. Therefore, the physical properties are improved by the interaction between polyaniline and activated carbon.
The polyaniline / activated carbon composite material is characterized by the combined capacity of the non-Faraday mechanism of activated carbon and the Faraday mechanism of the oxidation / reduction reaction of polyaniline. Therefore, it is possible to obtain a larger capacity than that obtained with the conventional activated carbon alone or with polyaniline alone.
Polyaniline may be formed in the form of a film or particles on the surface of the activated carbon. As in the conventional method, when polyaniline and carbon materials are made of a film by using an electrochemical method, a composite material synthesized in the form of a film is formed on a substrate, which is difficult to separate from an electrode and thus difficult to process and utilize. However, since the polyaniline / activated carbon composite material according to the chemical method according to the present invention may be formed in both a film and a particle form after drying, it may be manufactured in various ways depending on the intended use.
The specific surface area of the activated carbon is 100 m 2 / g or more, preferably 100 to 3,000 m 2 / g. If the specific surface area of the activated carbon is less than 100 m 2 / g, it is not preferable because the large specific surface area, which is an advantage of the activated carbon, cannot be used.
The content of the polyaniline is preferably 3 to 10 times the mass of the activated carbon. If the content of polyaniline is less than three times the mass of activated carbon, the composite material has the characteristic of activated carbon and the capacity of the composite material is not preferable. If the content of the polyaniline exceeds 10 times, the composite material has a strong characteristic of polyaniline. It is not preferable because the structural stability of the target composite material cannot be obtained.
Referring specifically to the production method of the present invention, an acid solution is first prepared. The acid solution may be an inorganic acid or an organic acid, the inorganic acid may be hydrochloric acid, bromic acid, sulfuric acid, phosphoric acid, nitric acid, carbonate, perchloric acid, boric acid, and the organic acid is N- [2-hydroxyethyl] piperazine-N'- [2-ethanesulfonic acid] (N- [2-hydroxyethyl] piperazine-N '-[2'-ethanesulfonic acid]), N-tris- [hydroxymethyl] methyl-2-aminoethanesulfonic acid (N-tris -[hydroxymethyl] methyl-2-aminoethanesulfonic acid), 1,4-piperazinediethanesulfonic acid, (3-N-morpholino) propanesulfonic acid ((3-N-morpholino propanesulfonic acid) and acetic acid.
Activated carbon is added to this acid solution. An acid solution containing activated carbon is stirred to form a uniformly dispersed activated carbon dispersion solution. The component ratio of the polyaniline / activated carbon composite material obtained depends on the amount of activated carbon added at this time. Stirring prevents aniline monomers from gathering together to form a stable structure, so the faster the stirring speed, the more polyvinyline in the form of a fiber is formed.
Aniline monomer is added and dispersed in the dispersion solution. Next, the polymerization initiator of the same molar concentration as the aniline monomer is added. The polymerization initiator is slowly added dropwise over 30 minutes. As the polymerization initiator, ammonium persulfate, potassium persulfate, sodium persulfate, Azoisobutylonitrile, and benzoyl peroxide may be used. As the polymer polymerization occurs, polyaniline is synthesized on the surface of activated carbon.
The temperature of the reaction system is kept below 5 ° C during the reaction. After stirring for 20 to 24 hours the resulting precipitate is filtered off and washed with ethanol and water. The synthesized material is dried in an oven for 20 to 24 hours. Thereby, the polyaniline / activated carbon composite material which concerns on this invention can be completed.
According to one aspect of the present invention, activated carbon is added to an acid solution, followed by stirring to disperse activated carbon, and aniline monomer is added and dispersed in the solution, and a polyaniline is formed on the surface of the activated carbon by adding a polymer polymerization initiator having the same molar concentration. Provides activated carbon composites.
1 illustrates a process of synthesizing polyaniline on the surface of activated carbon and a model of a polyaniline / activated carbon composite material. Referring to FIG. 1, it can be seen that aniline monomers existing around activated carbon are polymerized on the surface of activated carbon to form polyaniline. The polyaniline shape of such activated carbon surface may be formed in the form of a film or particles.
According to another aspect of the present invention, activated carbon is added to an acid solution, followed by stirring to disperse activated carbon, and aniline monomer is added and dispersed in the solution, and a polymer polymerization initiator of the same molar concentration is added to form polyaniline on the surface of the activated carbon. A capacitor electrode formed using a polyaniline / activated carbon composite material is provided.
Specifically, the polyaniline / activated carbon composite material of the present invention is mixed with a binder material, dispersed in a solvent, coated on a platinum electrode, dried, and used as a capacitor electrode. Here, the binder material, the solvent, and the like may be used a conventional binder material and solvent used in the manufacture of the capacitor electrode.
The amount of power storage in the case of using only activated carbon and the amount of energy storage in the case of using polyaniline alone is shown to be greater than the arithmetically added value when manufacturing the electrode using the polyaniline / active carbon composite material of the present invention. In the electrode using the polyaniline and activated carbon composite material, the capacity by the non-Faraday mechanism of activated carbon and the Faraday mechanism by the oxidation / reduction reaction of polyaniline are added, which is higher than the capacity that can be obtained when using activated carbon alone or using polyaniline alone. Indicates that larger doses can be obtained.
Hereinafter, the present invention will be described with reference to examples, which are exemplary but the scope of the present invention is not limited thereto.
Example
Example 1
To a 500 ml Erlenmeyer flask containing 300 ml of 1 M hydrochloric acid solution, 0.5 g of activated carbon (purchased from KURARAY CHEMICAL) was added. The activated carbon was stirred to disperse well in the hydrochloric acid solution. 5 ml of aniline monomer was added to the solution. The solution was stirred so that the aniline monomer was uniformly dispersed in the hydrochloric acid solution like activated carbon. 100 ml of 0.06 M ammonium persulfate aqueous solution was slowly added dropwise to the solution over 30 minutes using a dropping funnel. Erlenmeyer flasks were placed in a styrofoam box of water to maintain the temperature of the reaction system below 5 ° C. during the polymerisation. After stirring for 24 hours, the resulting precipitate was filtered and washed with ethanol and water. The synthesized material was dried in an oven at 60 ° C. for 24 hours to complete the polyaniline / activated carbon composite.
Example 2
The same procedure as in Example 1 was carried out except that the content of activated carbon was 1.0 g.
Example 3
The same procedure as in Example 1 was conducted except that the content of activated carbon was 1.5 g.
Comparative Example 1
Activated carbon RP-20 [purchased from KURARAY CHEMICAL] was used without any treatment. Detailed specification of activated carbon RP-20 is as follows.
Moisture Content: 0.4 wt%
Ach content: 0 wt%
PH: 8.1
Average particle size: 6.1 μm
Iodine adsorption capacity: 1970 mg / g
Benzene Adsorption: 56.0 wt%
Specific surface area: 1797 m 2 / g
Comparative Example 2
Polyaniline emeraldine salt (M N ca. 15,000) purchased from Sigma Aldrich was used.
Examples 1 to 3 and Comparative Examples 1 and 2 are collectively shown in Table 1.
Evaluation and Results
< Structural Analysis of Composite Materials>
X-ray Diffraction
X-ray diffraction analysis of Examples 1, 2 and 3 and Comparative Examples 1 and 2 were carried out using PANalytical's X'Pert PRO Diffractometer instrument under the following conditions.
X-ray: Cu
Voltage-Current: 40 kV-30 mA
Measuring angle range: 10 to 50 Theta
Step: 0.0170˚
The X-ray diffraction analysis (XRD) results of Examples 1, 2 and 3 are shown in FIG. 2, and the X-ray diffraction analysis (XRD) results of Comparative Examples 1 and 2 are shown in FIG. 3. It can be seen from the XRD graph of FIG. 3 that the characteristic peak of activated carbon is shown at 2θ = 43.2 °. 2 and 3, it can be seen that the crystal peak of the activated carbon in the Example is reduced than in Comparative Example 1 which is pure activated carbon. Table 2 shows the peak sizes of Examples 1, 2 and 3 and Comparative Examples 1 and 2 at 2θ = 43.2 °.
In polyaniline / activated carbon composites, the more polyaniline covers the surface of the activated carbon, the smaller the peak of activated carbon is. Referring to Table 2, it can be seen that in Examples 1, 2, and 3, more polyaniline is produced because the lower the amount of activated carbon characteristic peaks, the lower the amount of activated carbon is. As more activated carbon is added, the surface area of activated carbon becomes wider throughout the reaction system. Since the amount of the aniline monomer present in the reaction system is limited, the larger the amount of activated carbon, the more the aniline monomer is distributed in a larger area, thereby reducing the amount of aniline monomer present per unit area. This leads to the same result even when the polymerization reaction occurs and the aniline monomer is synthesized into polyaniline. On this principle, the composition ratio of the composite material can be changed depending on the amount of activated carbon added to the reaction system.
<Production of Electrode>
A small amount of sample suitable for attachment to the electrode is weighed out. Samples of Examples 1-3 and Comparative Examples 1,2 were mixed with 10 wt% of polyvinylidene fluoride (PVdF) binder, dispersed in NMP (NMethyl-pyrrolidone), and coated on a platinum electrode. This was dried and used as a working electrode.
< Electrochemical Characterization>
Cyclic voltammetry was measured using Potentiostat and IVIUM STAT. In a three-electrode battery system using a polyaniline / activated carbon composite material as a working electrode, Ag as a reference electrode, and Pt as a counter electrode, 0.5 M sulfuric acid aqueous solution was measured as an electrolyte. The measurement voltage ranged from 0 V to 1 V and voltage was applied at a rate of 0.005 V / s. Two cycles were measured for each sample, and the graph of the second cycle in which the circulating voltage current was stabilized was taken as the result. After converting the obtained result to 1 mg basis, the cyclic voltammetry graph of each sample was compared.
FIG. 4 shows cyclic voltammograms measurement results of Examples 1, 2 and 3, and FIG. 5 shows graphs showing cyclic voltage current measurement results of Comparative Examples 1 and 2. FIG. 4 and 5 are based on 1 mg of the sample. The capacity of Examples 1, 2 and 3 and Comparative Examples 1 and 2 obtained by cyclic voltammetry are shown in Table 3.
Referring to Table 3, it can be seen that in Example 1 to Example 3 synthesized by the method provided by the present invention, the total capacity is higher than that of Comparative Example 1. In particular, Examples 1 and 2 have a higher overall capacity than Comparative Example 2, and Example 1 has the highest overall capacity of all examples.
Example 1 and Example 2 showed the storage capacity larger than the arithmetic addition of the electrical storage amount of Comparative Example 1 (activated carbon) and Comparative Example 2 (polyaniline).
The amount of power storage of Example 3 to which the highest amount of activated carbon was added was the smallest, and the amount of power storage of Example 1 to which the smallest amount of activated carbon was added. It can be seen that the storage capacity is large when the content of activated carbon is smaller than that of polyaniline. In addition, it can be seen from these results that the total capacity of the composite material varies depending on the component ratio of polyaniline and activated carbon.
When the polyaniline / activated carbon composite material is synthesized by the method provided by the present invention, an electrode material capable of controlling the amount of storage can be prepared by adjusting the mixing ratio according to the amount of activated carbon introduced.
Claims (11)
Adding and dispersing aniline monomer in the dispersion solution, and adding a polymerization initiator having the same molar concentration; And
And a polyaniline synthesized on the surface of the activated carbon by a polymerization reaction.
Method for producing a polyaniline / activated carbon composite material, characterized in that the polyaniline is formed in the form of a film or particles on the surface of the activated carbon.
The specific surface area of the activated carbon is a method for producing a polyaniline / activated carbon composite material, characterized in that 100 to 3,000 m 2 / g.
The polyaniline content of the polyaniline / activated carbon composite material, characterized in that 3 to 10 times the mass of the activated carbon.
The acid solution is a method for producing a polyaniline / activated carbon composite material, characterized in that the inorganic or organic acid.
The inorganic acid is a method for producing a polyaniline / activated carbon composite material, characterized in that one selected from the group consisting of hydrochloric acid, bromic acid, sulfuric acid, phosphoric acid, nitric acid, carbonic acid, perchloric acid, boric acid.
Forming the polyaniline is a method for producing a polyaniline / activated carbon composite material comprising polymerizing the internal temperature at 5 ℃ or less for 20 to 24 hours, and filtering and washing the precipitate.
A polyaniline / activated carbon composite material in which polyaniline is formed in the form of a film or particles on the surface of the activated carbon by adding a polymer polymerization initiator having the same molar concentration.
The polyaniline content of the polyaniline / activated carbon composite material, characterized in that 3 to 10 times the mass of the activated carbon.
Polyaniline / activated carbon composite material, characterized in that the specific surface area of the activated carbon is 100 to 3,000 m 2 / g.
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| KR20180092683A (en) * | 2017-02-10 | 2018-08-20 | 한국과학기술원 | Carbon Hybrid Fiber having High Crystalline Conducting Polymer Shell and method of manufacturing the same |
| KR20190044313A (en) | 2017-10-20 | 2019-04-30 | 광주과학기술원 | Selenium-sulfur compound electrode material coated with polyaniline for lithium-sulfur battery and lithium-sulfur battery using the same |
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| KR20210120281A (en) * | 2020-03-26 | 2021-10-07 | 한국과학기술연구원 | Carbon body-conducting polymer composite, manufacturing method thereof, and zinc-polyaniline battery comprising the same |
| CN111705545B (en) * | 2020-06-29 | 2022-06-21 | 江苏奥神新材料股份有限公司 | Conductive polymer composite conductive paper and preparation method thereof |
| CN114709088A (en) * | 2022-04-13 | 2022-07-05 | 合肥工业大学 | Preparation of polyaniline/conductive carbon black composite material and construction of self-repairing high-voltage super-electric device |
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| KR20040106947A (en) * | 2003-06-05 | 2004-12-20 | 삼성전자주식회사 | Method for preparing a Conductive Film and a Pattern using Metallic Nano particle and Carbon Nanotube |
| KR20070021846A (en) * | 2005-08-20 | 2007-02-23 | 삼성에스디아이 주식회사 | Mesoporous carbon composite, manufacturing method thereof, and fuel cell using the same |
| KR100728611B1 (en) * | 2005-11-25 | 2007-06-14 | 주식회사 진우엔지니어링 | Catalyst for fuel cell electrode and method of preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20040106947A (en) * | 2003-06-05 | 2004-12-20 | 삼성전자주식회사 | Method for preparing a Conductive Film and a Pattern using Metallic Nano particle and Carbon Nanotube |
| KR20070021846A (en) * | 2005-08-20 | 2007-02-23 | 삼성에스디아이 주식회사 | Mesoporous carbon composite, manufacturing method thereof, and fuel cell using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20180092683A (en) * | 2017-02-10 | 2018-08-20 | 한국과학기술원 | Carbon Hybrid Fiber having High Crystalline Conducting Polymer Shell and method of manufacturing the same |
| KR101894899B1 (en) | 2017-02-10 | 2018-09-04 | 한국과학기술원 | Carbon Hybrid Fiber having High Crystalline Conducting Polymer Shell and method of manufacturing the same |
| KR20190044313A (en) | 2017-10-20 | 2019-04-30 | 광주과학기술원 | Selenium-sulfur compound electrode material coated with polyaniline for lithium-sulfur battery and lithium-sulfur battery using the same |
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