KR102033583B1 - Supercapacitor Electrode with Graphene and Fabrication Method Thereof - Google Patents
Supercapacitor Electrode with Graphene and Fabrication Method Thereof Download PDFInfo
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- KR102033583B1 KR102033583B1 KR1020120137795A KR20120137795A KR102033583B1 KR 102033583 B1 KR102033583 B1 KR 102033583B1 KR 1020120137795 A KR1020120137795 A KR 1020120137795A KR 20120137795 A KR20120137795 A KR 20120137795A KR 102033583 B1 KR102033583 B1 KR 102033583B1
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- graphene layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- 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 is a current collector; A graphene layer formed on one or both surfaces of the current collector; And an electrode active material layer formed on the graphene layer and containing an electrode active material, a conductive material, and a binder. The supercapacitor may dramatically improve output characteristics by lowering equivalent series resistance (ESR) in an electrode. An electrode and a method of manufacturing the same can be provided.
Description
The present invention relates to a supercapacitor electrode and a method of manufacturing the same.
Among the energy storage devices, a supercapacitor includes an electrode structure, a separator, and an electrolyte, and is attracting attention as a next generation energy storage device due to its fast charge and discharge rate, high stability, environmentally friendly characteristics, and high capacity electrical characteristics.
The electrode structure uses a current collector as a path through which electrons generated from an active material can move, and a method of directly applying and drying a slurry mixed with an active material, a conductive material, and a binder to the current collector, or rolling and applying a coated and dried active material sheet. It is manufactured by bonding to a current collector through a laminating process. However, the electrode structure manufactured as described above may be repeatedly peeled or discharged, and thus the active material layer may be peeled off from the current collector or the active material may be released, thereby increasing internal resistance and decreasing conductivity. Therefore, the content of the binder or the content of the active material should be increased. This requires a technique of using an adhesive between the active material layer and the current collector.
Korean Patent No. 0581232 discloses a conductive adhesive having excellent adhesion and conductivity. In controlling the viscosity of the coating liquid and the wettability with the current collector, it is difficult to coat the current collector with a thin and uniform thickness. Peeling or dissolution may occur. In addition, the Republic of Korea Patent Publication No. 2011-0111236 discloses the formation of a conductive layer through a polymerization reaction using a monomer, a crosslinking agent and a conductive material, but the binder content is high, there is a limit in improving the conductivity.
That is, the conventional electrode structure has a problem of high internal series resistance and low output characteristics of the electrode when forming the electrode without a conductive layer, the method using a conductive adhesive mixed with a conductive material and a polymer binder has been attempted to overcome this Although the current collector and the wettability is poor, there is a limitation in the formation of a conductive layer to achieve low thickness and low uniformity, and electrical conductivity is lowered due to the use of a binder, which makes it difficult to expect high energy density and output density.
It is an object of the present invention to provide a supercapacitor electrode and a method of manufacturing the same that can dramatically improve output characteristics by lowering equivalent internal resistance (ESR).
The present invention to achieve the above object is a current collector; A graphene layer formed on one or both surfaces of the current collector; And an electrode active material layer formed on the graphene layer and containing an electrode active material, a conductive material, and a binder.
In the supercapacitor electrode according to the exemplary embodiment of the present invention, the graphene layer may satisfy the following
(In
In the supercapacitor electrode according to an embodiment of the present invention, a conductive layer adhesive layer may be further included between the graphene layer and the electrode active material layer.
In the supercapacitor electrode according to the embodiment of the present invention, the graphene layer may be 0.3 nm to 30 nm.
In the supercapacitor electrode according to an embodiment of the present invention, the electrode active material is soft carbon, hard carbon, activated carbon, carbon, aerogel, polyacrylonitrile It may be a carbon-based compound such as (polyacrylonitrile), carbon nano fibers (carbon nano fibers), activated carbon nano fibers (activated carbon nano fibers), vapor grown carbon fibers (vapor grown carbon fibers).
In the supercapacitor electrode according to an embodiment of the present invention, the conductive material is Super-P Black, Carbon Black, Acetylene Black, Catchen Black, Activated Carbon, Hard Carbon, Soft It may be any one or a mixture of two or more selected from the group consisting of carbon, soft carbon, carbon nanotubes, and graphite.
In the supercapacitor electrode according to the embodiment of the present invention, the binder is selected from the group consisting of vinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile and polymethylmethacrylate. It may be any one or a mixture of two or more.
In the supercapacitor electrode according to the embodiment of the present invention, the current collector may be made of one or a mixture of two or more selected from the group consisting of nickel, cobalt, platinum, gold, aluminum, chromium and copper.
The present invention provides a step of forming a graphene layer by reacting by providing a reaction gas and heat containing a carbon source on the current collector, and
Forming an electrode active material layer on the graphene layer may provide a method of manufacturing a supercapacitor electrode comprising a.
In the method of manufacturing a supercapacitor electrode according to an embodiment of the present invention, the graphene layer may include satisfying the following
(In
In the method of manufacturing a supercapacitor electrode according to an embodiment of the present invention, a conductive adhesive layer may be further included between the graphene layer and the electrode active material layer.
In the method of manufacturing a supercapacitor electrode according to an embodiment of the present invention, the carbon source may be a carbon-containing compound having 1 to 10 carbon atoms.
In the method of manufacturing a supercapacitor electrode according to an embodiment of the present invention, the graphene layer may include forming by any one method selected from inductively coupled plasma chemical vapor deposition, low pressure chemical vapor deposition and atmospheric pressure chemical vapor deposition. have.
In the method of manufacturing a supercapacitor electrode according to an embodiment of the present invention, the deposition method may be carried out under a temperature of 900 ~ 1200 ℃ and pressure conditions of 1x10 -1 ~ 1x10 -3 Torr.
The supercapacitor electrode according to the present invention can significantly improve the output characteristics by lowering the equivalent internal series resistance (ESR), and has the advantage of excellent electrode characteristics and durability.
1 shows equivalent series resistance (ESR) in an electrode according to an embodiment of the present invention.
Figure 2 shows the power density (power density) according to an embodiment of the present invention.
Hereinafter, the supercapacitor electrode of the present invention will be described in detail. The embodiments and drawings introduced below are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art. In addition, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and the accompanying drawings. Descriptions of well-known functions and configurations that may be unnecessarily blurred are omitted.
The supercapacitor electrode according to the present invention has a graphene layer formed on a current collector, one surface or both surfaces of the current collector, and provides a supercapacitor electrode including an electrode active material layer on the formed graphene layer. In this case, the electrode active material layer includes an electrode active material, a conductive material and a binder.
In the supercapacitor electrode according to the exemplary embodiment of the present invention, the graphene layer satisfies
In
The supercapacitor electrode according to the embodiment of the present invention includes a current collector and a graphene layer formed on at least one surface of the current collector, and including an electrode active material layer on the formed graphene layer, wherein the conductive layer is conductive between the graphene layer and the electrode active material layer. Further comprising an adhesive layer to increase the bonding strength of the graphene layer and the electrode active material layer to reduce the interface resistance to increase the power density to improve the output of the battery as well as to improve the durability.
In the supercapacitor electrode according to the embodiment of the present invention, the thickness of the graphene layer is preferably 0.3 nm to 30 nm, which can be controlled in the type of current collector or graphene manufacturing process. The graphene layer may be composed of a multi-layer, wherein if more than 10 layers or more than 30nm, it may be difficult to form a graphene as a uniform layer with respect to the entire surface of the electrode, when graphene is not formed uniformly Interfacial resistance can be increased by defects in the liver.
In the case of the electrode active material according to an embodiment of the present invention, it is preferable to use a carbon material. Examples of the carbon material include natural graphite, artificial graphite, graphitized carbon fibers, non-graphite carbon, carbon nanotubes, and the like.
Conductive material according to an embodiment of the present invention is any one or a mixture of two or more selected from the group consisting of super-P, carbon black, acetylene black, caten black, activated carbon, hard carbon, soft carbon, carbon nanotubes and graphite It is not necessarily limited thereto.
The binder according to an embodiment of the present invention is selected from the group consisting of polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, poly vinylidene fluoride, polyacrylonitrile and polymethyl methacrylate It may be any one or a mixture of two or more, but is not necessarily limited thereto.
Electrode active material layer according to an embodiment of the present invention includes an active material, a conductive material and a binder, the weight mixing ratio thereof is preferably 10: 0.5 ~ 1: 0.1 ~ 0.5. When the content of the conductive material is increased compared to the content of the binder, the conductivity may be improved but the film may not be formed. On the contrary, when the content of the conductive material is reduced, it is difficult to expect the effect of sufficiently improving the conductivity.
The current collector according to an embodiment of the present invention is nickel (Ni), cobalt (Co), platinum (Pt), gold (Au), aluminum (Al), chromium (Cr), palladium (Pd) and copper (Cu) It may be made of any one or a mixture of two or more selected from the group consisting of, it is preferable to use nickel or aluminum.
The present invention provides a reaction gas containing a carbon source on the current collector, forming a graphene layer by reaction by heat, and
It provides a method of manufacturing a supercapacitor electrode comprising the step of forming an electrode active material layer on the graphene layer.
In the method of manufacturing a supercapacitor electrode according to an embodiment of the present invention, the reaction for forming a graphene layer on the current collector is raised to 900 ~ 1,200 ℃ at a temperature increase rate of 10 ℃ / min ~ 40 ℃ / min at room temperature Thereafter, a heat treatment process is carried out to stand at an elevated temperature for 30 minutes to 2 hours.
In addition, the cooling process may be performed for 30 minutes to 3 hours at room temperature after the heat treatment process. During the heat treatment process, carbon atoms which are raw materials of graphene are adsorbed to the current collector, and carbon atoms adsorbed to the current collector in the cooling process form the graphene electrode on the surface of the current collector. At this time, the thickness of the graphene can be adjusted by controlling the current collector material and the cooling process speed which can determine the adsorption amount of carbon atoms.
In the method of manufacturing a supercapacitor electrode according to an embodiment of the present invention, the graphene layer satisfies the following relational formula (1).
In
In the method of manufacturing a supercapacitor electrode according to an embodiment of the present invention, further comprising a conductive adhesive layer between the graphene layer and the electrode active material layer to increase the bonding strength of the graphene layer and the electrode active material layer to increase the power density by reducing the interface resistance Not only can the output of the battery be improved, but also the durability can be enhanced.
In the method of manufacturing a supercapacitor electrode according to an embodiment of the present invention, the graphene layer is formed by any one of deposition methods selected from inductively coupled plasma chemical vapor deposition, low pressure chemical vapor deposition, and atmospheric pressure chemical vapor deposition.
In the method of manufacturing a supercapacitor electrode according to an embodiment of the present invention, the deposition conditions are carried out under a temperature of 900 ~ 1,200 ℃ and pressure conditions of 1x10 -1 ~ 1x10 -3 Torr.
In the method of manufacturing a supercapacitor electrode according to an embodiment of the present invention, the carbon source may be a carbon containing compound having 1 to 10 carbon atoms, for example, carbon monoxide, carbon dioxide, methane, ethane, ethylene, ethanol, Acetylene, propane, propylene, butane, butylene, butadiene, pentane, pentene, pentine, pentadiene, cyclopentane, hexane, hexene, cyclohexane, cyclohexadiene, benzene, toluene and combinations thereof; It is not necessarily limited thereto.
Hereinafter, the present invention will be described in detail with reference to Examples.
(Example 1)
Nickel (Ni) foil was loaded into a quartz tube chamber and heated to 30 ° C./min up to 1,000 ° C., and then carbon and hydrogen containing gas (CH 4 : H 2 = 5: 20 sccm) at 1000 ° C. was subjected to 2 × 10 −2 torr pressure. After supplying for 1 hour, the graphene layer was formed on the nickel foil by chemical vapor deposition through a method of rapidly cooling the temperature in the chamber by moving and removing the heat source. Next, the activated carbon (YP80F), the conductive material (Super P), and the polyvinylidene fluoride (PVdF) were added to NMP, which is a solvent, in a weight ratio of 82: 10: 8, respectively. To prepare an electrode active material layer slurry. The slurry was coated on a current collector to a thickness of 100 μm using a bar coater, and then dried in a 75 ° C. convection oven for 1 hour, and then made into a coin cell, and then measured ESR, capacitance, energy characteristics, and output characteristics. It was.
(Comparative Example 1)
A coin cell was manufactured in the same manner as in Example 1 except that the graphene layer was not formed on the nickel foil as a current collector.
As shown in Table 1, Example 1 was confirmed that the ESR is improved by more than 60% compared to Comparative Example 1, due to the improvement of the ESR the output characteristics of Example 1 increased 1.72 times. Through this, it was confirmed that the supercapacitor electrode efficiency according to the present invention exhibits low ESR and high rate characteristics.
As described above in the present invention has been described by a limited embodiment, but this is only provided to help a more general understanding of the present invention, the present invention is not limited to the above embodiments, the present invention is not limited to the common knowledge Those having a variety of modifications and variations are possible from these descriptions.
Therefore, the spirit of the present invention should not be limited to the described embodiments, and all the things that are equivalent to or equivalent to the claims as well as the following claims will belong to the scope of the present invention. .
Claims (13)
(In relation 1, t 1 and t 2 are the thicknesses of the electrode active material layer and the graphene layer, respectively.)
The graphene layer is a 3 to 30 nm supercapacitor electrode.
The conductive material is a super-capacitor electrode of any one or two or more selected from the group consisting of super-P, carbon black, acetylene black, caten black, activated carbon, hard carbon, soft carbon, carbon nanotubes and graphite.
The binder is a supercapacitor electrode which is any one or a mixture of two or more selected from the group consisting of vinylidene fluoride-hexafluoropropylene copolymer, poly vinylidene fluoride, polyacrylonitrile and polymethyl methacrylate.
The current collector is a supercapacitor electrode made of any one or a mixture of two or more selected from the group consisting of nickel, cobalt, platinum, gold, aluminum, chromium and copper.
And forming an electrode active material layer on the graphene layer, wherein the graphene layer satisfies the following relational formula (1).
(In relation 1, t 1 and t 2 are the thicknesses of the electrode active material layer and the graphene layer, respectively.)
The method of manufacturing a supercapacitor electrode further comprising a conductive adhesive layer between the graphene layer and the electrode active material layer.
The carbon source is a method for producing a supercapacitor electrode is a carbon containing compound having 1 to 10 carbon atoms.
The graphene layer is a method of manufacturing a supercapacitor electrode formed by any one of the deposition method selected from inductively coupled plasma chemical vapor deposition, low pressure chemical vapor deposition and atmospheric pressure chemical vapor deposition.
The deposition method is a method of manufacturing a supercapacitor electrode that is carried out under a pressure condition of 1x10 -1 to 1x10 -3 Torr.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020120137795A KR102033583B1 (en) | 2012-11-30 | 2012-11-30 | Supercapacitor Electrode with Graphene and Fabrication Method Thereof |
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| KR1020120137795A KR102033583B1 (en) | 2012-11-30 | 2012-11-30 | Supercapacitor Electrode with Graphene and Fabrication Method Thereof |
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| KR102033583B1 true KR102033583B1 (en) | 2019-10-17 |
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| KR101897091B1 (en) | 2018-01-26 | 2018-09-10 | 가천대학교 산학협력단 | Flexible micro supercapacitor and method of manufacturing the same |
| KR20210035995A (en) | 2019-09-25 | 2021-04-02 | 한국과학기술연구원 | Current collector comprising graphene layer and lithium ion battery and supercapacitor containing the electron collector |
| RU2726945C1 (en) * | 2019-12-16 | 2020-07-17 | Общество с ограниченной ответственнотью "ИОН" | Flat supercapacitor based on carbon-carbon nanocomposite and method of its production |
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| KR100581232B1 (en) | 2003-08-27 | 2006-05-17 | (주)에스와이하이테크 | Electric Conduction Adhesive and Joined Electrode Using The Said Manufacturing Method thereof |
| KR101194716B1 (en) * | 2009-09-15 | 2012-10-25 | 주식회사 엘지화학 | Electrode for lithium secondary battery and Lithium secondary battery comprising the same |
| KR101279606B1 (en) * | 2009-12-11 | 2013-07-05 | 한국전자통신연구원 | Method for depositing graphene film |
| KR101227152B1 (en) | 2010-04-02 | 2013-01-28 | 롯데알미늄 주식회사 | Composition for forming conductive adhesive layer of electrode, manufacturing method of electrode, and electrode using the same |
| KR20120056556A (en) * | 2010-11-25 | 2012-06-04 | 삼성전기주식회사 | Multi layered electrodes and super capacitor comprising the same |
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