KR101614299B1 - Manufacturing method of ultracapacitor electrode with high density and supercapacitor cell using the ultracapacitor electrode manufactured by the method - Google Patents

Manufacturing method of ultracapacitor electrode with high density and supercapacitor cell using the ultracapacitor electrode manufactured by the method Download PDF

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KR101614299B1
KR101614299B1 KR1020150079583A KR20150079583A KR101614299B1 KR 101614299 B1 KR101614299 B1 KR 101614299B1 KR 1020150079583 A KR1020150079583 A KR 1020150079583A KR 20150079583 A KR20150079583 A KR 20150079583A KR 101614299 B1 KR101614299 B1 KR 101614299B1
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electrode
carbon nanomaterial
ultracapacitor
carbon
dispersion
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KR1020150079583A
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Korean (ko)
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노광철
강원섭
박선민
조민영
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한국세라믹기술원
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/36Nanostructures, e.g. nanofibres, nanotubes or fullerenes

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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The present invention relates to a method for manufacturing an ultracapacitor electrode, which includes a step of adding at least one carbon nanomaterial selected from graphene, a carbon nanotube and a carbon nanofiber, and a silane-based material to a dispersion medium to disperse the carbon nanomaterial, a step of filtering the dispersed materials with a vacuum filter on which follicles are mounted, a step of selectively filtering the carbon nanomaterial with the follicles and sticking the filtered carbon nanomaterial to the follicles in a rubber type electrode form, a step of separating the carbon nanomaterial in the rubber type electrode form from the follicles and drying the separated carbon nanomaterial, and a step of punching the dried material into a desired size, and an ultracapacitor cell using the ultracapacitor electrode manufactured thereby. According to the present invention, the ultracapacitor electrode having improved lifespan characteristics that requires only the carbon nanomaterial that is an electrode active material and does not require a binder and a conductive material is manufactured. A process is very simple as compared with a coating method or a rolling method for forming an electrode, and durability can be improved by improving the density of the electrode and an irreversible capacity can be reduced by minimizing an electron movement path loss.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing an ultracapacitor electrode having improved density and an ultra capacitor cell using the same, and a method of manufacturing an ultracapacitor cell using the same,

The present invention relates to a method of manufacturing an ultracapacitor electrode and an ultracapacitor cell to which an ultracapacitor electrode manufactured using the same is applied. More particularly, the present invention relates to a method of manufacturing an ultracapacitor electrode, The process is very simple as compared with the coating method or the rolling method for forming the electrode and the density of the electrode can be improved to improve the durability and the irreversible capacity can be reduced by minimizing the electron transfer path loss and the ultra- A capacitor electrode, and an ultra-capacitor cell using the ultra-capacitor electrode.

In general, an ultracapacitor is also referred to as an electric double layer capacitor (EDLC) or a supercapacitor, which is formed by a pair of electrodes and conductors, each having a different sign at the interface between the electrode and the electrolyte, (Electric double layer) of the charge / discharge operation is used, and the deterioration due to the repetition of the charging / discharging operation is very small, so that the device is not required to be repaired. Accordingly, ultracapacitors are mainly used for IC (integrated circuit) backup of various electric and electronic devices. Recently, they have been widely used for toys, solar energy storage, HEV (hybrid electric vehicle) have.

Such an ultracapacitor generally includes two electrodes of a positive electrode and a negative electrode impregnated with an electrolytic solution, a separator of a porous material interposed between the two electrodes to allow only ion conduction and to prevent insulation and short circuit, A gasket for preventing leakage of electricity and preventing insulation and short-circuit, and a metal cap as a conductor for packaging them. Then, one or more unit cells (normally 2 to 6 in the case of a coin type) are stacked in series and the two terminals of the positive and negative electrodes are combined.

The performance of the ultracapacitor is determined by the electrode active material and the electrolyte. In particular, the main performance such as the capacitance is largely determined by the electrode active material. As such an electrode active material, activated carbon is mainly used. Since porous activated carbon has a high specific surface area, it is widely used as an electrode active material for ultracapacitors which exhibits a capacity by physical adsorption and desorption of ions.

However, recently, the most difficult problem in manufacturing an electrode for an ultracapacitor is newly encountered in that it is difficult to increase the capacity per unit volume due to an electrode active material having a high specific surface area. That is, when activated carbon having a high specific surface area is used, the capacity per unit mass is increased, but the electrode density is reduced due to a high specific surface area, and a problem arises that the capacity is inferior to the unit volume.

Conventionally, two methods are mainly used in manufacturing an activated carbon electrode for an ultracapacitor.

In the first method, an activated carbon mixture in the form of slurry in which activated carbon, a binder, a conductive material, and a dispersion medium, which are electrode active materials, is mixed is coated on an aluminum foil, followed by drying and punching (Coating method).

In the second method, a paste-like activated carbon mixture obtained by mixing activated carbon, a binder, a conductive material, and a dispersion medium, which is an electrode active material, is drawn and rolled by two rolls to form a sheet, and then the sheet is cut or punched To thereby produce an electrode (rolling method).

FIG. 1 is a process diagram for explaining a method for manufacturing an electrode for an ultracapacitor (rolling method) according to the prior art, in which a paste-like activated carbon mixture is drawn and rolled into a sheet 10, The electrode 20 is manufactured by punching.

However, the conventional activated carbon electrode 20 manufactured as described above shows a limit in rolling the electrode due to porosity and high specific surface area of the activated carbon, and generally shows an electrode density of about 0.5 to 0.6 g / cm 3, This is a major factor in limiting the volume per volume.

Coating type electrodes are difficult to uniformly disperse when the dispersant is not added, and when coated on the copper foil, voids are formed to cause loss in the electron transport path, resulting in large irreversible capacity, which affects reduction in lifetime characteristics .

Conventional techniques for making rubber types without the addition of binders have the disadvantage that the surface is rough, slick, denser and less durable.

As the applications of ultracapacitors are expanded, higher non-storage capacities and energy densities are required, and it is required to develop an electrode active material exhibiting higher capacitive capacities or to develop new manufacturing methods.

Korean Patent Registration No. 10-1031227

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a coating method for forming an electrode without requiring a binder and a conductive material in addition to the carbon nanomaterial and the silane- The present invention provides a method of manufacturing an ultracapacitor electrode having an improved durability and reduced irreversible capacity through minimization of electron path loss and improved life characteristics, And an ultracapacitor cell using the ultra capacitor electrode manufactured using the same.

The present invention relates to a method for producing a carbon nanotube, comprising the steps of adding and dispersing at least one carbon nanomaterial selected from graphene, carbon nanotube, and carbon nanofiber and a silane-based material to a dispersion medium, and filtering the resultant dispersion with a vacuum filter equipped with a filter The carbon nanomaterial is selectively filtered by the follicle so that the filtered carbon nanomaterial is adhered to the fibril in the form of a rubber type electrode; Removing the fibrils from the follicles, drying the fibrils, and punching the dried product to a desired size.

The carbon nanomaterial preferably has a specific surface area ranging from 100 to 700 m < 2 > / g.

The silane-based material may be selected from the group consisting of (3-aminopropyl) triethoxysilane, aminopropyltrimethoxysilane, aminoalkylmethoxysilane, 3-methacryloxypropyl tri And may include at least one material selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, and 3-chloropropyltrimethoxysilane.

The silane-based material is preferably added in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the carbon nanomaterial.

The foliage has a mesh shape, and the mesh size of the mesh is preferably 10 nm to 20 m.

The dispersion may be carried out by ultrasonic treatment in order to remove impurities attached to the surface of the carbon nanomaterial from the surface and make the aggregated particles atomized and uniformly dispersed. The frequency of the ultrasonic wave to be injected is preferably 20 to 40 kHz Do.

The dispersion medium may be at least one selected from the group consisting of distilled water, ethanol, acetone, isopropyl alcohol, diethylene glycol, propylene glycol, acetonitrile, ethyl acetate, polycarbonate, N-methyl-2-pyrrolidone, dimethylsulfoxide and dimethylformamide Or more.

It is preferable to add the carbon nanomaterial to the dispersion medium so that the dispersion concentration of the carbon nanomaterial is 0.01 to 15.0 g / L.

The filtration step may further include a step of immersing the dispersion in a cleaning liquid and performing a washing process while stirring.

The present invention also provides a method of manufacturing a thin film capacitor, comprising: a positive electrode including an ultracapacitor electrode manufactured by the above manufacturing method; a negative electrode including an ultracapacitor electrode manufactured by the manufacturing method; and a negative electrode disposed between the positive electrode and the negative electrode, And a gasket for sealing the metal cap, wherein the anode, the separator, and the cathode are disposed inside the metal cap, and the metal cap is filled with an electrolyte solution. .

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a first separator for preventing a short circuit, an anode including the ultracapacitor electrode manufactured by the manufacturing method, a second separator for preventing short- A negative electrode including the prepared ultracapacitor electrode is wound in the form of a roll in the form of a coiled roll, a first lead wire connected to the negative electrode, a second lead wire connected to the positive electrode, A metal cap and a sealing rubber for sealing the metal cap, wherein the roll revolver is impregnated with an electrolytic solution.

According to the present invention, a binder and a conductive material are not required in addition to the carbon nanomaterial and the silane-based material, which are electrode active materials, and the process is much simpler than the coating method and the rolling method for forming the electrode, An ultracapacitor electrode having a high capacity per volume can be manufactured. The density of the electrode is improved, so that it is possible to integrate the electrode, thereby increasing the capacity per unit volume. A device for coating or a device for rolling is not necessary and a vacuum type filter is used to form a rubber type in the process of removing the solvent, so that a separate molding step is not necessary and manufacturing cost can be reduced.

Coating type electrodes are difficult to uniformly disperse when a dispersant is not added, and when coated on a copper foil, voids are formed and a loss occurs in the electron transport path, resulting in a large irreversible capacity, which affects a reduction in lifetime characteristics The conventional technique of producing a rubber type without adding a binder has a disadvantage in that the surface is rough, is not smooth, has a low density, and has poor durability. In the present invention, a silane having advantages of adhesiveness, dispersion and surface modification It is possible to improve the durability and minimize the irreversible capacity by minimizing the electron path loss, and to manufacture an ultracapacitor electrode having improved lifetime characteristics.

According to the present invention, a film type rubber-type ultracapacitor electrode is manufactured using ultrasonic waves and a vacuum filter to minimize the movement path loss of electrons and reduce the irreversible capacity, thereby achieving more efficient and stable lifetime characteristics .

1 is a process diagram for explaining a method of manufacturing an ultracapacitor electrode according to the prior art.
2 is a cross-sectional view of a coin type ultracapacitor according to an example.
3 to 6 are views showing a winding type ultracapacitor according to an example.
7 is an optical microscope photograph of an ultracapacitor electrode manufactured according to an experimental example.
8 is a scanning electron microscope (SEM) photograph of an ultracapacitor electrode manufactured according to an experimental example.
9 is an optical microscope photograph of an ultracapacitor electrode manufactured according to Comparative Example 1. Fig.
10 is an optical microscope photograph of an ultracapacitor electrode manufactured according to Comparative Example 2. Fig.
11 is a scanning electron microscope (SEM) photograph of an ultracapacitor electrode manufactured according to Comparative Example 2. Fig.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not. Wherein like reference numerals refer to like elements throughout.

Hereinafter, the term "nano" refers to a size in nanometers (nm), meaning a size of 1 to 1,000 nm, and a nanofiber refers to a fiber having a diameter of 1 to 1,000 nm And the nanomaterial is used as a material having a diameter of 1 to 1,000 nm.

A method of manufacturing an ultracapacitor electrode according to a preferred embodiment of the present invention includes the steps of adding and dispersing at least one carbon nanomaterial selected from graphene, carbon nanotube, and carbon nanofiber and a silane- A step of filtering the dispersion product with a vacuum filter equipped with a filter; and a step of selectively filtering the carbon nanomaterial by the filter cloth and filtering the filtered carbon nanomaterial into a rubber type electrode. Removing the carbon nanomaterial in the form of a rubber-type electrode from the follicle and drying, and punching the dried product to a desired size.

The carbon nanomaterial preferably has a specific surface area ranging from 100 to 700 m < 2 > / g.

The silane-based material may be selected from the group consisting of (3-aminopropyl) triethoxysilane, aminopropyltrimethoxysilane, aminoalkylmethoxysilane, 3-methacryloxypropyl tri And may include at least one material selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, and 3-chloropropyltrimethoxysilane.

The silane-based material is preferably added in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the carbon nanomaterial.

The foliage has a mesh shape, and the mesh size of the mesh is preferably 10 nm to 20 m.

The dispersion may be carried out by ultrasonic treatment in order to remove impurities attached to the surface of the carbon nanomaterial from the surface and make the aggregated particles atomized and uniformly dispersed. The frequency of the ultrasonic wave to be injected is preferably 20 to 40 kHz Do.

The dispersion medium may be at least one selected from the group consisting of distilled water, ethanol, acetone, isopropyl alcohol, diethylene glycol, propylene glycol, acetonitrile, ethyl acetate, polycarbonate, N-methyl-2-pyrrolidone, dimethylsulfoxide and dimethylformamide Or more.

It is preferable to add the carbon nanomaterial to the dispersion medium so that the dispersion concentration of the carbon nanomaterial is 0.01 to 15.0 g / L.

The filtration step may further include a step of immersing the dispersion in a cleaning liquid and performing a washing process while stirring.

An ultracapacitor cell according to a preferred embodiment of the present invention includes an anode including the ultracapacitor electrode manufactured by the manufacturing method, an anode including the ultracapacitor electrode manufactured by the manufacturing method, And a gasket for sealing the metal cap, wherein the metal cap is disposed inside the anode, the separator and the cathode, and the electrolyte is injected into the metal cap.

According to another aspect of the present invention, there is provided an ultracapacitor cell including: a first separator for preventing a short circuit; an anode including an ultra-capacitor electrode manufactured by the manufacturing method; and a first electrode for preventing short- 2 separator and an anode including the ultracapacitor electrode manufactured by the manufacturing method described above are sequentially stacked to form a coiled roll, a first lead wire connected to the negative electrode, and a second lead wire connected to the positive electrode, A metal cap for accommodating the roll revolver, and a sealing rubber for sealing the metal cap, wherein the roll revolver is impregnated with the electrolyte solution.

Hereinafter, a method of manufacturing an ultracapacitor electrode according to a preferred embodiment of the present invention will be described in more detail.

In the present invention, at least one carbon nanomaterial selected from graphene, carbon nanotube (CNT), and carbon nanofiber is used as an electrode active material. Such a carbon nanomaterial preferably has a specific surface area of about 100 to 700 m 2 / g.

Graphene is a term made by combining graphite, which means graphite, and suffix -ene, which means a molecule having a double bond of carbon. Three out of four outermost electrons constituting graphene form a sp 2 hybrid orbital, forming a strong covalent σ bond, while the remaining one electron forms a π bond with other carbons around it, Shape 2-dimensional structure. The single-layer graphene has a thickness of about 0.34 nm and is very thin and has excellent mechanical strength, thermal and electrical properties, flexibility and transparency.

The fracture stress of graphene is ~ 40 N / m, the theoretical limit value is about 125 GPa, and the modulus of elasticity is about ~ 1.0 TPa which is more than 200 times of steel. This is because there is a hard carbon bond and there is no bond in the fault. It can also be increased by 20% in a plane axis direction, which is much higher than any other crystal. Also, as temperature rises, graphene continues to shrink by two-dimensional phonons, and at the same time it has a very flexible, yet well-cracked characteristic when pulled strongly.

Graphene has a thermal conductivity of about 5,000 W / m · K at room temperature, which is superior to carbon nanotubes or diamond. It is 50% higher than carbon nanotubes and 10 times larger than metals such as copper and aluminum. This is because graphene can easily transmit atomic vibrations. This excellent thermal conductivity also affects the long average free path of electrons. On the other hand, graphite with graphene laminate has a disadvantage in that the thermal conductivity (about 100 times) is significantly lowered in the vertical direction.

The maximum electron mobility of graphene at room temperature is 200,000 cm 2 / Vs. This is known to be due to the very small degree of scattering of electrons in the case of graphene, which leads to a long average free path. Therefore, resistance is lower than 35% of copper with very low resistance. Also, in the case of graphene, it does not lose its electrical conductivity even when the area is increased or decreased by more than 10%.

Grapin became widely known as Novoselov and Professor Geim of the University of Manchester announced the world's first method of separating graphene from pencil lead graphite using the adhesion of Scotch tape. First, prepare graphite flakes, conventional scotch tape, and SiO 2 wafers. The prepared flakes are put on a scotch tape and folded several times and repeated. After this process is completed, the tape is placed on a SiO 2 wafer, rubbed off the remaining flake marks, and the tape is removed to obtain a multi-layered graphene from one layer of graphene.

The reason why this method is possible is to look at the atomic structure of graphene. Graphene has three carbon atoms forming a strong covalent bond on a two-dimensional plane, while a relatively weak van der Waals force in the vertical direction, resulting in very low coefficient of friction between layers, resulting in weak adhesion of the scotch tape It becomes possible to separate it. The exfoliated graphene was very simple to prepare for the sample, and exhibited excellent electrical and structural properties, which played a role in rapidly spreading the basic research of graphene. However, since the area is only micrometer level and the yield is low, there is a limit to the manufacturing method for various applications.

The chemical stripping method is a method based on a solvent that uses an oxidation and reduction reaction and is the closest to the two goals of large area growth and mass production of graphene. To induce peeling through the production of graphite oxide and then to improve the electrical characteristics of the graphene oxide through reduction. There have been many studies on the oxidation of graphite, but the method proposed by Hummers is the most used. This method is easy to mass-produce graphene and is a graphene manufacturing method which can be applied to various applications.

The graphenes mentioned above may be of a single layer, a double layer or a multilayer type, but it is preferable to use a multilayer type graphene because single layer or double layer graphene is difficult to manufacture and expensive to purchase.

Carbon nanotubes (CNTs) have a rounded form of hexagonal networks of carbon atoms. At this time, the horses have a jig shape and an arm chair shape at the end according to the angle. In addition, the rounded shape has a single wall structure with a single wall and a multi wall structure with multiple walls. In addition, a single wall or a multi wall Wall (Nano tube bundle), and a metal-atom-filled nano tube. The diameter of the carbon nanotubes is preferably from 5 nm to 1 占 퐉, and more preferably from 20 nm to 1 占 퐉.

The carbon nanofiber has a fiber shape and preferably has an aspect ratio (length / diameter) of about 10 to 1,000. The diameter of the carbon nanofibers is preferably 5 nm to 1 mu m, more preferably 20 nm to 1 mu m or so.

One or more carbon nanomaterials selected from graphene, carbon nanotubes, and carbon nanofibers and a silane-based material are added to a dispersion medium and dispersed.

The silane-based material may be selected from the group consisting of (3-aminopropyl) triethoxysilane, aminopropyltrimethoxysilane, aminoalkylmethoxysilane, 3-methacryloxypropyl tri 3-Methacryloxypropyltrimethoxysilane, Methyltrimethoxysilane, 3-Chloropropyltrimethoxysilane, a mixture thereof, and the like. When such a silane-based material is added to the carbon nanomaterial, it has advantages such as improved adhesion and surface modification, and can improve the density and durability of the electrode. In addition, such a silane-based material may play a role in allowing the carbon nanomaterial to adhere well to the follicle during the filtration process by a vacuum filter described later. By adding a small amount of a silane-based material having advantages such as adhesion, dispersion and surface modification, it is possible to improve the densities of the electrodes and to reduce the irreversible capacity by minimizing the electron path loss, An ultracapacitor electrode can be manufactured. The silane-based material is preferably added in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the carbon nanomaterial.

The dispersion medium may be selected from the group consisting of distilled water, ethanol, acetone, isopropyl alcohol (IPA), diethyleneglycol (DEG), propylene glycol (PG), acetonitrile ), Ethyl acetate, polycarbonate (PC), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO) Dimethylformamide (DMF), and mixtures thereof.

It is preferable to add the carbon nanomaterial to the dispersion medium so that the dispersion concentration of the carbon nanomaterial is about 0.01 to 15.0 g / L, and more preferably about 0.1 to 10.0 g / L. The dispersion is preferably performed at a stirring speed of about 10 to 300 rpm for 10 minutes to 24 hours.

It is preferable that the dispersion is performed by ultrasonic treatment so as to achieve uniform dispersion. Graphene, carbon nanotubes, and carbon nanofibers are very difficult to disperse uniformly without the use of dispersants, and when carbon nanomaterials are not uniformly dispersed, vacancies arise, resulting in loss of electron transport paths, A capacity is generated, which greatly affects the life characteristics. When the ultrasonic treatment is performed, uniform dispersion of the carbon nanomaterial can be realized. The ultrasonic treatment not only removes impurities adhering to the surface of the carbon nanomaterial from the surface but also serves to atomize the aggregated particles and uniformly disperse them. The empty space is not generated by the ultrasonic wave treatment, so that the loss of the movement path of the electrons can be minimized, and the irreversible capacity can be reduced to provide stable lifetime characteristics. The frequency of the ultrasonic wave to be scanned may be about 20 to 40 kHz, and the ultrasonic wave is preferably applied for about 10 minutes to 6 hours. Generally, ultrasound refers to a sound wave having a frequency of 20 kHz or more.

The dispersion process (dispersion of the carbon nanomaterial and the silane-based material) may be immersed in a cleaning liquid such as ethanol, and the cleaning process may be performed while stirring. The stirring speed is preferably about 10 to 500 rpm, and the stirring time is preferably about 10 minutes to 24 hours.

The dispersion product is filtered with a vacuum filter equipped with a filter. A vacuum filter is a device for wrapping a filter cloth and applying vacuum to the back surface to suck moisture in the sludge. Generally, it is a drum type and a belt type. A typical drum type is an Oliver filter. The vacuum filter may be a commercially available vacuum filter. The degree of vacuum of the vacuum filter may be about 10 -2 to 100 torr, which is lower than the atmospheric pressure, but is not limited thereto. The fibrils selectively filter the carbon nanomaterials, and the filtered carbon nanomaterials stick to the fibrils in the form of rubber type electrodes. Carbon nanomaterials larger than the pore size of the filter paper can not pass through the follicles during filtration by the vacuum filter and are attached to the follicles. The follicle has a mesh shape, and the hole size of the mesh is preferably about 10 nm to 20 m in consideration of the size of the carbon nanomaterial.

The carbon nano material, which is an electrode type of a rubber type, is removed from the fibrils and dried. The drying is preferably performed at a temperature of about 40 to 150 ° C. The drying is preferably carried out at the above temperature for about 10 minutes to 48 hours. Such a drying process evaporates the remaining dispersion medium and binds the carbon nanomaterial particles to improve the strength of the ultracapacitor electrode.

The dried product is punched to a desired size (e.g., 12 mm) to form an ultracapacitor electrode.

As described above, a film type rubber type ultracapacitor electrode is manufactured by using an ultrasonic wave and a vacuum filter to minimize the movement path loss of electrons and reduce the irreversible capacity to provide a more efficient and stable lifetime characteristic .

The ultracapacitor electrode manufactured as described above can be applied to coin-type ultracapacitors or wound capacitors with high capacity. Hereinafter, a coin-type ultracapacitor and a wound-up capacitor according to an example will be described in detail.

FIG. 2 is a sectional view of a coin-type ultracapacitor cell to which the ultra-capacitor electrode 10 is applied, according to an embodiment of the present invention. 2, reference numeral 190 denotes a metal cap as a conductor, 160 denotes a porous separator for insulation and short circuit between the anode 120 and the cathode 110, 192 denotes leakage of electrolyte And to prevent insulation and short circuit. At this time, the anode 120 and the cathode 110 are firmly fixed by the metal cap 190 and an adhesive.

The coin-type ultracapacitor cell includes an anode 120 made of the above-described ultracapacitor electrode, a cathode 110 made of the above-described ultracapacitor electrode, a cathode 110 disposed between the anode 120 and the cathode 110, A separator 160 for preventing a short circuit between the anode 120 and the cathode 120 is disposed in the metal cap 190 and an electrolyte solution in which the electrolyte is dissolved is injected between the anode 120 and the cathode 110 , And gasket (192).

The separator may be a battery such as a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyester nonwoven fabric, a polyacrylonitrile porous separator, a poly (vinylidene fluoride) hexafluoropropane copolymer porous separator, a cellulose porous separator, a kraft paper or a rayon fiber, And is not particularly limited as long as it is a membrane commonly used in the field.

On the other hand, the electrolyte filled in the ultracapacitor is a nonaqueous system in which at least one solvent selected from propylene carbonate (PC), acetonitrile (AN) and sulfolane (TE) is mixed with tetraethylammonium tetrafluoborate (TEABF4) (triethylmethylammonium tetrafluoborate) may be used. The electrolytic solution may contain at least one ionic liquid selected from 1-ethyl-3-methyl imidazolium tetrafluoroborate (EMIBF4) and 1-ethyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide.

FIGS. 3 to 6 are views showing an ultracapacitor cell according to another example, and a method of manufacturing the ultracapacitor cell will be described in detail with reference to FIGS. 3 to 6. FIG.

As shown in FIG. 3, lead wires 130 and 140 are attached to an anode 120 and a cathode 110, respectively, which are ultracapacitor electrodes.

4, the first separator 150, the anode 120, the second separator 160, and the working electrode 110 are laminated and coiled to form a roll- (175), and wound around the roll with an adhesive tape (170) or the like so that the roll shape can be maintained.

The second separator 160 between the anode 120 and the cathode 110 prevents shorting between the anode 120 and the cathode 110. The first and second separation membranes 150 and 160 may be formed of any one of a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyester nonwoven fabric, a polyacrylonitrile porous separator, a poly (vinylidene fluoride) hexafluoropropane copolymer porous separator, a cellulose porous separator, Or a separator commonly used in the field of batteries and capacitors such as rayon fibers.

As shown in FIG. 5, a sealing rubber 180 is mounted on a roll-shaped resultant and is mounted on a metal cap (for example, an aluminum case (Al Case) 190).

The electrolytic solution is injected so that the roll-shaped winding element 175 (the anode 120 and the cathode 110) is impregnated and sealed. The electrolytic solution is selected from among tetraethylammonium tetrafluoborate (TEABF4) and triethylmethylammonium tetrafluoborate (TEABF4) in at least one solvent selected from propylene carbonate (PC), acetonitrile (AN) and sulfolane One in which at least one kind of salt is dissolved can be used. The electrolytic solution may contain at least one ionic liquid selected from 1-ethyl-3-methyl imidazolium tetrafluoroborate (EMIBF4) and 1-ethyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide.

The ultracapacitor cell 100 fabricated in this manner is schematically shown in Fig.

Hereinafter, experimental examples according to the present invention will be specifically shown, and the present invention is not limited to the following experimental examples.

<Experimental Example>

0.5 g of carbon nanotubes (CNT) and 0.05 g of (3-aminopropyl) triethoxysilane were added to 80 ml of diethyleneglycol (DEG) and dispersed. The dispersion was uniformly dispersed using an ultrasonic treatment. The ultrasonic treatment was performed for 1 hour. The ultrasonic wave treatment was performed using a device having an output of 300 W and a frequency of 20 kHz. The carbon nanotubes used were multi-wall carbon nanotubes (MWCNTs) of Carbon Nano-material Technology Co., Ltd. and had a diameter of about 5 to 20 nm And a length of about 10 mu m.

The ultrasonic treated carbon nanotube dispersion was immersed in 1 liter of anhydrous ethanol and stirred. The stirring speed was 200 rpm, and the stirring time was 30 minutes.

The dispersion product was filtered with a vacuum filter equipped with a filter cloth. Only the carbon nanotubes are selectively filtered by the follicles, and the filtered carbon nanotubes stick to the follicles. Carbon nanotubes larger than the pore size of the filter paper can not pass through the follicles during filtration by the vacuum filter, and are attached to the follicles. The follicle had a mesh shape, and the hole size of the mesh was about 5 탆.

The follicles were separated from the vacuum filter and the carbon nanotubes were separated from the rubber type electrodes attached to the follicles.

The carbon nanotubes separated from the follicles were dried in a dryer at 80 ° C for 12 hours.

The carbon nanotube ultracapacitor electrode was obtained by punching a rubber-type electrode with a diameter of 12 mm, and an optical microscope photograph thereof is shown in FIG. 8 is a scanning electron microscope (SEM) photograph of an ultracapacitor electrode manufactured according to an experimental example.

Comparative examples are presented to more easily grasp the characteristics of the experimental example. It is to be noted that the comparative examples described below are merely presented for comparison with the characteristics of the experimental examples and are not prior art of the present invention.

&Lt; Comparative Example 1 &

The same carbon nanotubes as used in the experimental examples were prepared.

The carbon nanotubes, the binder and the dispersion medium were mixed to form an ultracapacitor electrode. This will be described in more detail.

0.95 g of carbon nanotubes, 0.05 g of a binder and 80 ml of a dispersion medium were mixed in a planetary mixer for 30 minutes to prepare a slurry composition for an ultracapacitor electrode. The binder used was polyvinylidenefluoride (PVDF). The dispersion medium used was N-methylpyrrolidone (NMP).

The composition for the ultracapacitor electrode was mixed for about 30 minutes, an appropriate amount of copper foil was removed, and then coated and adjusted in thickness using a doctor blade to form an electrode.

The electrode-shaped product was dried. The drying was carried out at a temperature of 80 DEG C for 30 minutes to 1 hour.

9 is an optical microscope photograph of an ultracapacitor electrode manufactured according to Comparative Example 1. Fig.

7 and 9, it was observed that the ultracapacitor electrode manufactured according to Comparative Example 1 was not dense, but the ultracapacitor electrode manufactured according to Experimental Example was observed to have a dense high density.

&Lt; Comparative Example 2 &

0.5 g of carbon nanotubes (CNT) was added to 80 ml of distilled water and dispersed. The dispersion was uniformly dispersed using an ultrasonic treatment. The ultrasonic treatment was performed for 1 hour. The ultrasonic wave treatment was performed using a device having an output of 300 W and a frequency of 20 kHz. The carbon nanotubes used were multi-wall carbon nanotubes (MWCNTs) of Carbon Nano-material Technology Co., Ltd. and had a diameter of about 5 to 20 nm And a length of about 10 mu m.

The dispersion product was filtered with a vacuum filter equipped with a filter cloth. Only the carbon nanotubes are selectively filtered by the follicles, and the filtered carbon nanotubes stick to the follicles. Carbon nanotubes larger than the pore size of the filter paper can not pass through the follicles during filtration by the vacuum filter, and are attached to the follicles. The follicle had a mesh shape, and the hole size of the mesh was about 5 탆.

The follicles were separated from the vacuum filter and the carbon nanotubes were separated from the rubber type electrodes attached to the follicles.

The carbon nanotubes separated from the follicles were dried in a dryer at 80 ° C for 12 hours.

The carbon nanotube ultracapacitor electrode was obtained by punching with a diameter of 12 mm, and an optical microscope photograph thereof is shown in FIG. 11 is a scanning electron microscope (SEM) photograph of an ultracapacitor electrode manufactured according to Comparative Example 2. Fig.

7 and FIG. 10, it was observed that the ultracapacitor electrode manufactured according to Comparative Example 2 was not dense, but the ultracapacitor electrode manufactured according to Experimental Example was observed to have a dense high density.

8 and 11, it was confirmed that the ultracapacitor electrode manufactured according to Experimental Example was dense and had less pores than the ultracapacitor electrode manufactured according to Comparative Example 2.

The characteristics of the ultracapacitor electrode prepared according to the experimental example and the ultracapacitor electrode prepared according to the comparative example 2 are shown in Table 1 below.

division Comparative Example Experimental Example Thickness (㎛) 75 76 Volume (cc) 0.0085 0.0086 Electrode weight (g) 0.0017 0.0022 Electrode density (g / cc) 0.20 0.26

The non-storage capacities of the cells assembled using the ultracapacitor electrode manufactured according to the experimental example and the ultracapacitor electrode prepared according to the comparative example 2 are shown in Table 2 below. The cell used was 1M TEABF4 (tetraethylammonium tetrafluoborate) / acetonitrile (AN) as the electrolyte, and the cell type was 2032 coin cells.

Cycle The non-storage capacity (F / cc) of the battery assembled using the ultracapacitor electrode manufactured according to the comparative example The non-storage capacity (F / cc) of the battery assembled using the ultracapacitor electrode manufactured according to Experimental Example One 11.02 14.76 20 10.99 14.70 40 10.96 14.66 60 10.95 14.66 80 10.94 14.63 100 10.91 14.62

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, This is possible.

110: cathode 120: anode
130: first lead wire 140: second lead wire
150: first separator 160: second separator
170: Adhesive tape 175: Winding element
180: sealing rubber 190: metal cap
192: Gasket

Claims (11)

Adding at least one carbon nanomaterial selected from graphene, carbon nanotubes, and carbon nanofibers and a silane-based material to a dispersion medium and dispersing the dispersion;
Filtering the dispersion product with a vacuum filter equipped with a filter;
The carbon nanomaterial is selectively filtered by the follicles, and the filtered carbon nanomaterial is adhered to the follicle in the form of a rubber type electrode;
Removing the carbon nanomaterial in the form of a rubber type electrode from the follicle and drying the carbon nanomaterial; And
And punching the dried product to a desired size.
The method of claim 1, wherein the carbon nanomaterial is a material having a specific surface area in the range of 100 to 700 m 2 / g.
The method of claim 1, wherein the silane-based material is selected from the group consisting of (3-aminopropyl) triethoxysilane, aminopropyltrimethoxysilane, aminoalkylmethoxysilane, Characterized in that it comprises at least one substance selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane and 3-chloropropyltrimethoxysilane. A method of manufacturing an ultracapacitor electrode.
The method of claim 1, wherein the silane-based material is added in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the carbon nanomaterial.
The method according to claim 1, wherein the follicle has a mesh shape and the mesh has a hole size of 10 nm to 20 m.
The carbon nanomaterial according to claim 1, wherein the dispersion is performed by removing ultrasonic waves from the surface of the carbon nanomaterial and removing the impurities from the surface of the carbon nanomaterial, thereby finely dispersing and dispersing the coagulated particles uniformly,
Wherein the frequency of the ultrasonic wave to be scanned is 20 to 40 kHz.
The method of claim 1, wherein the dispersion medium is selected from the group consisting of distilled water, ethanol, acetone, isopropyl alcohol, diethylene glycol, propylene glycol, acetonitrile, ethyl acetate, polycarbonate, N- Formamide. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
The method according to claim 1, wherein the carbon nanomaterial is added to the dispersion medium such that the dispersion concentration of the carbon nanomaterial is 0.01 to 15.0 g / L.
The method of claim 1,
Further comprising the step of immersing the dispersion in a cleaning liquid and performing a cleaning process while stirring the dispersion.
A positive electrode comprising an ultracapacitor electrode manufactured by the method of claim 1;
A negative electrode comprising an ultracapacitor electrode manufactured by the method of claim 1;
A separation membrane disposed between the anode and the cathode and for preventing a short circuit between the anode and the cathode;
A metal cap in which the anode, the separator, and the cathode are disposed and into which an electrolyte is injected; And
And a gasket for sealing the metal cap.
A first separator for preventing a short circuit, an anode including an ultracapacitor electrode manufactured by the method described in claim 1, and a second separator for preventing a short circuit between the anode and the cathode, A winding element in which a negative electrode including the ultracapacitor electrode is stacked and formed in a coiled roll shape;
A first lead wire connected to the negative electrode;
A second lead wire connected to the positive electrode;
A metal cap for receiving the book revolver; And
And a sealing rubber for sealing the metal cap,
Wherein the roll revolver is impregnated in an electrolytic solution.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101815898B1 (en) * 2016-09-08 2018-01-08 한국세라믹기술원 Manufacturing method of ultracapacitor electrode and ultracapacitor using the electrode
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KR20190053346A (en) * 2017-11-10 2019-05-20 한국세라믹기술원 Supercapacitor having excellent stability for high voltage and method for manufacturing the same
KR20200046556A (en) * 2018-10-25 2020-05-07 한국세라믹기술원 Electrolyte of supercapacitor, high voltage supercapacitor and manufacturing method of the high voltage supercapacitor using the electrolyte
WO2022075822A1 (en) * 2020-10-08 2022-04-14 상명대학교산학협력단 Electric double-layer capacitor in which self-discharge is suppressed and manufacturing method therefor
KR20220055899A (en) * 2020-10-27 2022-05-04 한국세라믹기술원 Manuafcturing method of electrode for energy storage device having effect of improving biocompatibility and energy storage device including the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015037125A (en) 2013-08-13 2015-02-23 太陽誘電株式会社 Electrode active material and electrochemical device including the same
KR101494622B1 (en) 2013-05-08 2015-02-23 한국세라믹기술원 Composite for supercapacitor electrode and manufacturing method of supercapacitor electrode using the composite

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101494622B1 (en) 2013-05-08 2015-02-23 한국세라믹기술원 Composite for supercapacitor electrode and manufacturing method of supercapacitor electrode using the composite
JP2015037125A (en) 2013-08-13 2015-02-23 太陽誘電株式会社 Electrode active material and electrochemical device including the same

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KR20200046556A (en) * 2018-10-25 2020-05-07 한국세라믹기술원 Electrolyte of supercapacitor, high voltage supercapacitor and manufacturing method of the high voltage supercapacitor using the electrolyte
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WO2022075822A1 (en) * 2020-10-08 2022-04-14 상명대학교산학협력단 Electric double-layer capacitor in which self-discharge is suppressed and manufacturing method therefor
KR20220055899A (en) * 2020-10-27 2022-05-04 한국세라믹기술원 Manuafcturing method of electrode for energy storage device having effect of improving biocompatibility and energy storage device including the same
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