KR20110000099A - Supercapacitor and method for making the same - Google Patents
Supercapacitor and method for making the same Download PDFInfo
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- KR20110000099A KR20110000099A KR1020090057467A KR20090057467A KR20110000099A KR 20110000099 A KR20110000099 A KR 20110000099A KR 1020090057467 A KR1020090057467 A KR 1020090057467A KR 20090057467 A KR20090057467 A KR 20090057467A KR 20110000099 A KR20110000099 A KR 20110000099A
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Classifications
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention is a supercapacitor for a thin film formed by spray coating carbon nanotube powder (or a thin film formed by spray coating a mixture of carbon nanotubes and different kinds of conductive powder or a thin film in which sprayed and laminated carbon nanotubes and different kinds of conductive powder, respectively). Supercapacitor comprising a carbon nanotube electrode configured to perform a function of the electrode (supercapacitor) to express a high energy density, power density and fast charge and discharge rate (charger and discharge rate) and a manufacturing method thereof will be.
The present invention is a solid electrolyte layer; And an electrode layer formed by spray coating of carbon nanotube powder on both surfaces of the solid electrolyte layer; Structure consisting of; An insulating material for packing the entire structure; And electrical wires contacted and fixed to each of the double-sided electrode layers of the structure such that current flows. It provides a supercapacitor configured to include.
In another aspect, the present invention comprises the steps of preparing a structure by forming an electrode layer by carbon nanotube powder spray coating on both sides of the solid electrolyte layer; (b) contacting and fixing the electric wires so that a current flows in each of the double-sided electrode layers of the structure; And (c) packing the structure with insulating material; It provides a supercapacitor manufacturing method comprising a.
Supercapacitor, electrolyte layer, electrode layer, carbon nanotube, spray coating
Description
The present invention is a supercapacitor for a thin film formed by spray coating carbon nanotube powder (or a thin film formed by spray coating a mixture of carbon nanotubes and different kinds of conductive powder or a thin film in which sprayed and laminated carbon nanotubes and different kinds of conductive powder, respectively). Supercapacitor comprising a carbon nanotube electrode configured to perform a function of the electrode (supercapacitor) to express a high energy density, power density and fast charge and discharge rate (charger and discharge rate) and a manufacturing method thereof will be.
Supercapacitors (also known as electrical double-layer capacitors; ultracapacitors) were first introduced by General Electric's engineers in 1957 to immerse a porous carbon electrode in a liquid electrolyte to produce electricity. Since its introduction (US Patent No. 2,800,616 ("Low voltage electrolytic capacitor"), the structure of carbon paste electrodes, separators and electrolytes by Standard Oil Corporation (US Patent 3,536,963 ("Electrolytic capacitor having carbon paste electrodes")) Developed into a supercapacitor.
Supercapacitors have an energy density of about 100 times that of a traditional capacitor, about 100 to 1,000 times that of a secondary battery, power density, short charge and discharge speed, and long life. Cycle (long life cycle;> 100,000 cycles (charge-discharge)), such as safety, but there is a disadvantage that the energy density (energy density) is only about 1/10 compared to the secondary battery.
Therefore, in order to express the energy density of a supercapacitor to a secondary battery or more, and to manufacture a supercapacitor having a high power density, it has been concentrated on researching materials such as electrodes, electrolytes, and separators, and in particular, it is possible to replace the conventional carbon electrode. Much research has been conducted on new electrode materials, a method for manufacturing the electrode materials, a method for combining the materials, and the like.
Conventional electrode materials include: 1) metals and metal oxides; Zn, Co, Ni, Li, Ru, TiO 2 , PbO 2 , RuO 2 , IrO 2 , MnO 2 , Fe 3 O 4 , In 2 O 3 , WO 3 , SnO 2 , V 2 O 5 , Ni (OH) 2, Ni (OOH), LiCoO 2, Li 4 Ti 5 O 2, Ir 0 0 .7 .3 Mn O 2, etc., 2), carbon materials (carbonaceous materials); Graphite, carbon black, carbon nanotube, fullerenes, carbon cloth, foams, aerogels, etc. 3) conducting polymers ); polyaniline, polythiophene, polypyrrol and PEDOT. In particular, carbon nanotubes, which are used as electrode materials of the supercapacitors, have been noted as potential materials for improving power density and energy density of supercapacitors due to their excellent physical and chemical properties. A study on supercapacitors using electrodes was published in 1997 by Niu et al. (C. Niu, EK Sichel, R. Hoch, D. Moy, and H. Tennent, “High power electrochemical capacitors based on carbon nanotube electrodes ", Applied Physics Letters , vol. 70, no. 11, 1480-1482, Mar. 17, 1997) reported for the first time an electrode of an electric double layer capacitor including carbon nanotubes grown using a catalyst with improved performance over a conventional activated carbon electrode. Since then, a number of papers (RZ Ma et. Al., "Study of electrochemical capacitors utilizing carbon nanotube electrodes", Journal of Power Sources , vol. 84, 126-129, 1999; Kay Hyeok An et al., "Electrochemical properties of high-power supercapacitors using single-walled carbon nanotube electrodes", Advanced Functional Materials , vol. 11, no. 5, 387-392, 2001; Ch. Emmenegger et al., "Investigation of electrochemical double-layer (ECDL) capacitors electrodes based on carbon nanotubes and activated carbon materials", Journal of Power Sources , vol. 124, 321-329, 2003).
Hereinafter, a brief description will be made of conventional technologies related to a supercapacitor including a carbon nanotube electrode.
1. Carbon nanotube paste ( paste ) Supercapacitors with Electrodes
The supercapacitor is a paste or mixture of carbon nanotubes in a dispersion solvent and a binder to form a paste solution, and includes an electrode coated on a current collector by printing, spraying, etc., a binder or an adhesive. It is to fill a void (porosity) of the carbon nanotubes or prevent reducing the specific surface area of the carbon nanotube (specific area) energy density (E; EαCV i 2/2 ; where, C is the capacitance (capacitance), V i is the initial voltage; C∝εA / d, where ε is the permittivity of the electrolyte, A is the specific surface area of the carbon nanotubes, and d = the double-layer thickness of Helmholtz. , Power density (P; P = V i / (4R) due to an increase in contact resistance of the carbon nanotube paste and the current collector and high resistance due to impurities in the solvent and binder, where V i is an initial voltage voltage, R is equivalent series resistance There is a disadvantage in that internal resistance is reduced, and there is a problem in durability due to weak adhesion between the carbon nanotubes and the current collector.
(1) Korean Patent Registration No. 0558171 ("Method of manufacturing polarizable electrode using carbon nanotube and electric double layer capacitor using the same") is a polarization electrode of carbon nanotube to compensate for the low electrical conductivity which is a disadvantage of organic electrolyte. As a technique for producing a method, the activated carbon is added to an organic solution in which a ball milled carbon nanotube is mixed with a binder and an organic solvent, and the electrode in the form of a slurry sheet is pressed with a roll press. An electrode manufacturing method for heat treatment has been introduced.
(2) Republic of Korea Patent Publication No. 10-2007-0005611 ("electrode manufacturing method, electrode manufactured by the method and a supercapacitor comprising the electrode"; PCT / FR2005 / 000525) carbon nanotubes and active carbon ) Is a paste mixed with a powder material, a polymer binder, and a dispersing material, and used as an electrode of a supercapacitor.
(3) In the paper by Martti Kaempgen et al. ("Printable thin film supercapacitors using single-walled carbon nanotubes", Nano Letters , 06 April 2009), single-walled carbon nanotubes (SWCNT; A thin flexible carbon nanotube supercapacitor composed of a sprayed carbon nanotube electrode and a PVA / H 3 PO 4 polymer electrolyte or a H 3 PO 4 liquid electrolyte was introduced. In particular, the paper points out that the internal resistance of SWCNT films and electrolytes produced by the printer process is higher than that of commercial supercapacitors.
The improvement of the above-described techniques (1) to (3) is to lower the internal resistance of the carbon nanotube paste, the electrolyte and the contact resistance (internal resistance), and improve the adhesion between the current collector and the carbon nanotube. The energy density and power density of the supercapacitor must be improved. In addition, there is a disadvantage in that a material other than the carbon nanotubes of the paste (solution) fills the pores of the carbon nanotubes and blocks the pores of the carbon nanotubes, thereby preventing the ions of the electrolyte from freely moving.
2. Carbon nanotube composite ( composite ) Supercapacitors with Electrodes
(1) Korean Patent No. 0487069 ("Supercapacitor Using Electrode of New Material and Manufacturing Method"; US Patent No. 6,454,816 ("Supercapacitor using electrode of new material and method of manufacturing the same") Form an electrode in pellet form using a binder (a polymer resin such as polyvinylalcohol resin, polytetrafluoroethylene resin, phenol resin, carboxymethyl cellulose resin, etc.), or thermochemical It has been described as a technique capable of directly growing carbon nanotubes on a current collector using a deposition method or a microwave plasma chemical vapor deposition method to use as an electrode of a supercapacitor and lowering the internal resistance of the supercapacitor through post-treatment.
(2) Korean Patent Registration No. 0432486 ("Method for producing electrodes of high power supercapacitors using carbon nanotubes and supercapacitors using them") is a combination containing carbon nanotubes and polyvinylidene chloride. A supercapacitor comprising the prepared electrode is provided.
(3) Korean Patent Registration No. 0765615 ("Manufacturing Method of Pseudo-Capacitor Using Composite Material") is a method of chemically treating manganese oxide on the surface of carbon material (carbon black, carbon nanotube, vapor-grown carbon fiber (VGCF)) as an electrode active material. It is coated with a thickness of several nm by a phosphorous method, and chemically coated potassium permanganate (KMnO 4 ) on a carbon material, and PVDF (polyvinylidene fluoride) and acetylene black, respectively as a binder and a conductive material on the manganese oxide / carbon composite material To form an electrode of a manganese oxide / carbon composite material for pseudocapacitors, so that most of the manganese oxide contributes to the specific storage capacity, thereby increasing the electrochemical utilization of the manganese oxide, and A method of manufacturing a pseudo capacitor using a composite material maximizing the effect of improving conductivity is presented.
(4) US Pat. No. 7,061,749 ("Supercapacitor having electrode material comprising single-wall carbon nanotubes and process for making the same") is a single-wall carbon nanotube and polymer composite electrode. Presented a supercapacitor comprising a.
(5) RZ Ma et al.'S paper ("Study of electrochemical capacitors utilizing carbon nanotube electrodes", Journal of Power Sources, vol. 84, 126-129, 1999) includes a carbon nanotube composite electrode. We introduced a supercapacitor. Specifically, a composite electrode obtained by mixing 15% by weight of phenolic resin (PF) and 85% by weight of carbon nanotube, and molding the composite at an arbitrary pressure under 100 ° C. for 15 minutes, The electrode was carbonized at 850 ° C. for 2-4 hours in nitrogen (N 2 ) and the carbonized molding composite was immersed in sulfuric acid and nitric acid for 15 minutes and then washed with distilled water. Three supercapacitors of dried carbon nanotube / phenolic resin composite electrodes were introduced.
As described in the above (1) to (5), a supercapacitor composite electrode made of a mixture of carbon nanotubes and other materials has a high internal resistance, and thus there is a limit in improving power density and energy density.
3. Supercapacitors including carbon nanotube electrodes grown on a catalyst
The supercapacitor comprising a carbon nanotube electrode grown with a catalyst forms a catalyst on the current collector and heats the substrate to break the hydrocarbon precursor by thermal and chemical reactions. The present invention relates to a sputtering method for depositing carbon nanotubes on a current collector using a method of growing and a target. By the way, the vertically grown carbon nanotubes have a shape of about 500 to 1,000 times the length compared to the diameter, are easily collapsed by internal and external shocks, and the durability of the carbon nanotubes is weak due to the weak adhesive strength between the current collector and the carbon nanotubes. In addition, the contact resistance is large, the power density is low, there is a disadvantage of using expensive equipment. In addition, the slow growth rate of carbon nanotubes affects the manufacturing process speed, which leads to an increase in production cost.
(1) Korean Patent Registration No. 0449142 ("Micro supercapacitor using carbon nanotubes and a method of manufacturing the same") is a thin film containing carbon nanotubes using sputtering, thermo-deposition, or vacuum vapor deposition. A thin film of a solid electrolyte and an electrode composed of Li 3 PO 4 , LiPO 3 , LiBO 2 , LiO 2 , B 2 O 3 , V 2 O 5 , P 2 O 5 , SiO 2 or a mixture thereof between the electrodes and the two electrodes, respectively A micro-supercapacitor including current collectors of a thin film made of a metal on a back surface corresponding to a solid electrolyte of is provided.
(2) Korean Patent No. 0461966 ("Carbon Nanotube Electrodes, Electric Double Layer Capacitors Using the Same and Method for Manufacturing the Same") is a plasma chemical vapor deposition method for producing an electric double layer capacitor supercapacitor by growing carbon nanotubes directly on a metal substrate. The effective means for synthesizing carbon nanotubes, but the plasma chemical vapor deposition method has a limit to lengthen the length of carbon nanotubes, and the process of coating a separate catalytic metal thin film layer on a metal substrate by a process combining plasma chemical vapor deposition and thermal plasma chemical vapor deposition. It has been suggested to produce an electric double layer supercapacitor capable of growing a long carbon nanotube without using it and also using it as an electrode.
4. EPD ( electrophoretic deposition Supercapacitor comprising a carbon nanotube electrode manufactured by
PCT / US2005 / 042226 (WO 2007/053155 "High power density supercapacitors with carbon nanotube electrodes") is a metal substrate current collector by coating carbon nanotubes using an electrophoretic deposition (EPD) method on a metal substrate without a binder. A supercapacitor is proposed to effectively reduce the contact resistance between the CNT and the CNT electrode. Specifically, after preparing a solution in which carbon nanotubes are dispersed in a solvent, voltage is applied to the carbon nanotubes, the metal substrate is immersed in the solution, and carbon nanotubes on the metal substrate using the EPD method. A technique has been proposed for coating a tube and baking the carbon nanotube electrode under hydrogen gas to form an electrode of a supercapacitor.
5. SCBD ( supersonic cluster - beam deposition Supercapacitor comprising a carbon electrode manufactured by
In L. Diederich et al.'S paper (“Supercapacitors based on nanostructured carbon electrodes grown by cluster-beam deposition”), nanostructured carbon films were fabricated on the aluminum plate (current collector) using a cluster beam coating method. By increasing the adhesion between the carbon electrodes, the contact resistance can be reduced and the power density can be increased, and through the above method, the pores of the nanostructured carbon electrodes can be mesopore (20) to smoothly move the ions of the electrolyte. ~ 50mW), macropore (> 50kW) size, supercapacitor that can realize high energy density was introduced.
6. Other
In PCT / US2008 / 004593 (WO 2008/124167, "Charge storage devices containing carbon nanotube film as electrodes and charge collectors"), in conventional charge storage devices, a metal current collector and a carbon nanotube active electrode are generally combined. Unlike the structure of, it forms a nanowire structure containing carbon nanotubes (graphene, silver nanowires), which acts as an active material and a charge collector. A charge storage device that can perform simultaneously is presented. Specifically, a method of manufacturing a nanostructure comprising the carbon nanotubes; 1) filter cake produced from carbon nanotube suspension, 2) air brush pistol or inkjet printing of carbon nanotube and solution of active electrode material, 3) nanowire (tube) and active electrode A composite composed of an active material; The charge storage device formed by the present invention is presented.
As described above, matters to be improved in the conventional supercapacitor including the carbon nanotube electrode may be summarized as follows.
Iii) the internal resistance (contact resistance) of the carbon nanotubes and electrolytes should be reduced, ii) the adhesion between the current collector and the carbon nanotubes is improved, and the durability is improved. The pores should be larger than the ion size, i) increase the power density, energy density and charge / discharge rate of the supercapacitor.
An object of the present invention is to provide a supercapacitor that has improved energy density, reduced internal resistance (contact resistance), and improved power density and durability (direct coupling force).
In order to improve the energy density of the supercapacitor, the electrode layer is formed by spray coating carbon nanotube powder directly on both sides of the solid electrolyte. The electrode layer may be formed by spray coating a mixture of carbon nanotubes and different kinds of conductive powder or spray coating and coating carbon nanotubes and different kinds of conductive powder, respectively. In this case, the internal resistance of the electrode layer may be reduced to improve power density and durability (direct coupling force) of the supercapacitor.
1, the supercapacitor according to the present invention is spray coated with carbon nanotube powder on both surfaces of the solid electrolyte layer to form an electrode layer as shown in FIG. 1, and an electric wire is contacted and fixed to the electrode layer. It can manufacture by packing the structure which consists of an electrolyte layer and an electrode layer with an insulating material. These supercapacitors have high bonding strength due to the direct bonding of the carbon nanotube electrode layer and the solid electrolyte layer, thereby improving durability, and reducing the Helmholtz double-layer thickness to increase the capacity of the shaft (energy density). have. In addition, the internal resistance or the contact resistance is reduced to improve the power density.
In addition, the present invention is a mixture of carbon nanotubes and heterogeneous conductive powder on both sides of the solid electrolyte as shown in [2] spray coating electrode layer or a solid electrolyte, carbon as shown in [FIG. 3] Nanotubes, different types of conductive powder is provided with a supercapacitor provided with an electrode layer sequentially spray-coated. In this case, power density and energy density can be further improved by the large specific surface area (1,000 to 2,000 m 2 / g) of the heterogeneous conductive powder (carbon black, etc.).
On the other hand, before packing the structure with an insulating material, the pores of the carbon nanotubes are formed into mesopore sizes (20 to 50 microseconds) through heat treatment at 60 to 1,000 ° C., so that the electrolyte ions are transferred to the electrode including the carbon nanotubes. It can be smooth and the energy density can be improved.
As a method of spray coating the carbon nanotube powder, heterogeneous conductive powder, and a solid electrolyte powder, conventional solid phase powder deposition methods (aerosol deposition (AD), cold spray, etc.) may be used. However, in order to satisfy the spray coating conditions such as the coating critical speed of the powder, direct bonding force between substrates, uniformity, continuous, large area, etc., the inventors have previously applied the invention ("Korean Patent Application No. 2008-0072119" solid powder continuous Deposition apparatus and solid powder continuous deposition method " " " Korean Patent Application No. 2009-0038240 " solid powder coating apparatus " "
In addition, in order to improve the spray coating efficiency of the carbon nanotube powder, the inventors of the present invention have already filed an application ("Korean Patent Application No. 2008-0105104" Carbon Nanotube Cutting Dispersion Method and Apparatus "-Damage to the carbon nanotube itself). It is desirable to apply a pretreatment technique to minimize and disperse defects.
According to the present invention can improve the problems raised in the supercapacitor including the existing carbon nanotube electrode, it is possible to obtain the following specific effects.
First, it is possible to improve the power density of the supercapacitor by reducing the contact resistance (internal resistance) between the carbon nanotube powder, the current collector, the solid electrolyte, and the substrate (conductive and non-conductive) using the powder spray coating method.
Second, the adhesion between the carbon nanotube powder and the substrate and each layer (excellent), it is possible to solve the problem of durability degradation due to the adhesion force raised in the prior art to improve the durability of the supercapacitor.
Third, since no binder or glue is used, the specific surface area of the carbon nanotubes is maintained as it is without filling or clogging the voids of the carbon nanotubes, and the porosity is maintained at a size of 20 to 50 kPa. As a result, the ions of the electrolyte may move faster to the electrode including the carbon nanotubes, thereby improving the charge / discharge rate of the supercapacitor.
Fourth, because the electrode can be manufactured by spray coating a carbon nanotube powder and at least one mixed heterogeneous conductive powder, the supercapacitor can be maintained by maintaining the excellent conductivity (reduced internal resistance) and a large specific surface area of the electrode. It is possible to improve the power density and energy density.
Fifth, the electrode material of the supercapacitor may be mixed with carbon nanotubes or carbon nanotubes and one or more kinds of heteroconductive powders to prepare a flexible supercapacitor electrode of a thin film spray-coated on a conductive or nonconductive substrate.
Sixth, the direct coupling between the carbon nanotubes and the solid electrolyte reduces the double-layer thickness of Helmholtz, thereby improving the capacitance of the supercapacitor (energy density).
Seventh, it can be produced by a relatively simple manufacturing method of the powder spray coating method it can shorten the manufacturing time.
Hereinafter, the present invention will be described in detail with the accompanying drawings.
The present invention is a solid electrolyte (solid electrolyte) layer; And an electrode layer formed by spray coating of carbon nanotube powder on both surfaces of the solid electrolyte layer; Structure consisting of; An insulating material for packing the entire structure; And electric wires contacting the double-sided electrode layers of the structure such that current flows. It provides a supercapacitor configured to include.
The solid electrolyte layer is introduced between the electrode layer and the electrode to prevent short circuit between the two electrodes and to allow free ion exchange. In the present invention, by directly coupling with the carbon nanotube electrode layer to reduce the Helmholtz double-layer thickness (ion radius absorbed from the electrode and the electrolyte contact surface) to increase the capacitance (energy density), carbon nanotube electrode The direct bond between the solid electrolyte and the solid electrolyte improves durability. Polymer materials that can be used as solid electrolytes include polyacrylonitrile (PAN), polyvinyl chloride (PVC), polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), and polypropylene (PPO). oxide), polyvinyl sulfone (PVS), polyvinyl pyrrolidone (PVP), and the like.
The electrode layer formed by spray coating of carbon nanotube powder on both surfaces of the solid electrolyte layer has an electrical conductivity in order to increase the power density by reducing the internal resistance in order for the carbon nanotube to perform the electrode function. This excellent carbon nanotubes can be selectively used, and for this purpose, it is preferable to use carbon nanotube powder having an electrical conductivity of 100 to 10,000 S / cm.
The electrode layer may be formed by spray coating or spray coating each of carbon nanotube powder and heterogeneous conductive powder. In this case, the contact resistance and internal resistance of the supercapacitor are reduced, thereby improving power density. The heterogeneous conductive powders include Al, Zn, Co, Ni, Li, Ru, TiO 2 , PbO 2 , RuO 2 , IrO 2 , MnO 2 , Fe 3 O 4 , In 2 O 3 , WO 3 , SnO 2 , V 2 O 5, Ni (OH) 2, Ni (OOH), LiCoO 2, Li 4 Ti 5 O 2, Ir 0 .3 Mn 0 .7 O 2 , etc. of metal powder and metal compound powder, graphite (graphite), carbon One or more of carbonaceous materials powders such as carbon black and fullerenes, and conductive polymers powders such as polyaniline, polythiophene, polypyrrol, and PEDOT may be applied.
Meanwhile, when the structure is coated such that the electrolyte layer and the electrode layer are alternately repeated, the energy density of the supercapacitor is improved, and the above structure may be formed on the conductive or nonconductive substrate.
The present invention comprises the steps of: (a) preparing a structure by forming an electrode layer by carbon nanotube powder spray coating on both sides of the solid electrolyte layer; (b) contacting and fixing an electric line so that current flows in each of the double-sided electrode layers of the structure; And (c) packing the structure with insulating material; It provides with a supercapacitor manufacturing method comprising a.
Step (a) comprises the steps of (a-1) preparing a solid electrolyte layer; And (a-2) spray-coating carbon nanotube powder on both surfaces of the solid electrolyte layer to form a structure in which an electrode layer is formed. Can be implemented. The solid electrolyte layer may be made by mixing electrolyte powder and various materials. As an example of the step (a-1), the solid electrolyte layer may be mixed with water and phosphoric acid in a solid electrolyte powder such as PVA (polyvinyl alcohol) powder. After evaporation, water may be evaporated to prepare a solid electrolyte layer.
In addition, the step (a) comprises the steps of (a-1 ') preparing a conductive or non-conductive substrate; (a-2 ') spray coating the carbon nanotube powder on the substrate to form a lower electrode layer; (a-3 ') spray coating the electrolyte powder on the lower electrode layer to form a solid electrolyte layer; And (a-4 ′) spray coating carbon nanotube powder on the solid electrolyte layer to form an upper electrode layer. Can be implemented.
Step (b) is a step of contacting and fixing the electric wires so that a current flows in each of the double-sided electrode layers of the structure. 4 illustrates a state in which electric wires are contacted and fixed to various embodiments of the supercapacitor. As shown, when the layer formed on the upper or lower portion of the electrode layer is a non-conductive layer, the electric line must be directly in contact with and fixed to the electrode layer. However, when the layer formed on the upper or lower portion of the electrode layer is the conductive layer, the electric line is conductive. It can be selectively contacted and fixed to a layer or an electrode layer. This is because the electric wire and the electrode layer can be electrically connected through the conductive layer.
Step (c) is a step of packing the structure with an insulating material. In the step (c) it may further comprise the step of heat treatment at 60 ~ 1,000 ℃ before packing the structure with an insulating material. Through such heat treatment, the surface of the electrode layer is activated, and the specific surface area is increased, so that the ions of the electrolyte are absorbed and moved well into the pores of the electrode layer (pore size of 20 to 50Å) to improve the capacitance (energy density) and charge / discharge rate. can do.
Electrode formed by spray coating the carbon nanotube powder as described above (or electrode coated with a mixed spray coating of carbon nanotubes and different types of conductive powder, electrodes laminated with carbon nanotubes and different types of conductive powder, respectively) are super according to the present invention. In addition to performing the electrode function of the capacitor, it can be used as an electrode such as fuel cells, primary batteries (primary batteries) and secondary batteries (secondary batteries), solar cells (solar cells).
Although the present invention has been described with reference to the accompanying drawings as mentioned above, various modifications and variations are possible within the scope without departing from the spirit of the present invention, and can be used in various fields. Therefore, the claims of the present invention include modifications and variations that fall within the true scope of the invention.
1 is a schematic diagram showing a method of manufacturing a supercapacitor of the present invention prepared by spraying carbon nanotube powder on both surfaces of a solid electrolyte to form an electrode, and finishing with electric wire contacting, fixing, and insulating material packing.
FIG. 2 is a schematic diagram illustrating a supercapacitor structure in which an electrode is formed by spray coating a mixture of carbon nanotube powder and heterogeneous conductive powder on both surfaces of a solid electrolyte.
FIG. 3 is a schematic diagram showing various structures of a supercapacitor including an electrode laminated by spray coating a carbon nanotube powder and a heterogeneous conductive powder on both surfaces of a solid electrolyte.
FIG. 4 illustrates a supercapacitor structure of the present invention including a spray coated layer of a carbon nanotube or a powder mixed with carbon nanotubes and a heterogeneous conductive powder and a spray coated layer of a solid electrolyte powder on a conductive or nonconductive substrate. It is a schematic diagram.
5 is a schematic diagram illustrating a supercapacitor structure in which an electrode layer and a solid electrolyte layer are repeatedly stacked on a conductive and nonconductive substrate.
<Explanation of symbols on main parts of the invention>
10: electrode layer (carbon nanotube powder spray coating layer)
11: electrode layer (coating layer in which carbon nanotube powder and heterogeneous conductive powder are mixed and sprayed)
12: coating layer sprayed with different kinds of conductive powder
20
22: insulation material
31 carbon
33: non-conductive substrate
Claims (11)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR200472934Y1 (en) * | 2013-03-25 | 2014-05-30 | 맥슨 아이피 엘엘씨. | Straight magic iron with Curling iron |
| WO2016171407A1 (en) * | 2015-04-21 | 2016-10-27 | 고려대학교 산학협력단 | Supercapacitor and manufacturing method therefor |
| KR20190080202A (en) | 2017-12-28 | 2019-07-08 | 부산대학교 산학협력단 | Metal-organic composite comprising metal oxide and organic ligand, electrode for super-capacitor using the same, and method for preparing the same |
| KR102048151B1 (en) * | 2018-07-03 | 2019-11-22 | 울산대학교 산학협력단 | Method for manufacturing super-capacitor |
-
2009
- 2009-06-26 KR KR1020090057467A patent/KR20110000099A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR200472934Y1 (en) * | 2013-03-25 | 2014-05-30 | 맥슨 아이피 엘엘씨. | Straight magic iron with Curling iron |
| WO2016171407A1 (en) * | 2015-04-21 | 2016-10-27 | 고려대학교 산학협력단 | Supercapacitor and manufacturing method therefor |
| KR20190080202A (en) | 2017-12-28 | 2019-07-08 | 부산대학교 산학협력단 | Metal-organic composite comprising metal oxide and organic ligand, electrode for super-capacitor using the same, and method for preparing the same |
| KR102048151B1 (en) * | 2018-07-03 | 2019-11-22 | 울산대학교 산학협력단 | Method for manufacturing super-capacitor |
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