KR102013173B1 - Composite for ultracapacitor electrode, manufacturing method of ultracapacitor electrode using the composite, and ultracapacitor manufactured by the method - Google Patents

Abstract

The present invention, 0.1 to 20 parts by weight of a conductive material with respect to 100 parts by weight of the electrode active material, 100 parts by weight of the electrode active material, 1 to 20 parts by weight of the binder relative to 100 parts by weight of the electrode active material, 0.1 to 10 parts by weight of additives based on 100 parts by weight of the electrode active material 100 parts by weight to 100 parts by weight of the dispersion and 100 parts by weight of the electrode active material, wherein the additives include vinyl butyl ether, vinyl ethyl ether, vinyl iso butyl ether, and vinyl iso butyl ether. ), A composition for an ultracapacitor electrode comprising at least one material selected from the group consisting of vinyl methyl ether and styrene monomers, a method for producing an ultracapacitor electrode using the same and the method It relates to a manufactured ultracapacitor. According to the present invention, by using a small amount of additives with the binder, the contact with other raw materials is good, the resistance is low, the density increase and the durability are improved, so that excellent cell efficiency can be exhibited.

Description

A composition for an ultracapacitor electrode, a method of manufacturing an ultracapacitor electrode using the same, and an ultracapacitor manufactured by using the same method, the present invention relates to an ultracapacitor electrode using the composite, and ultracapacitor manufactured by the method.

The present invention relates to a composition for an ultracapacitor electrode, a method for producing an ultracapacitor electrode, and an ultracapacitor, and more particularly, by using a small amount of an additive together with a binder, good contact with other raw materials, low resistance, and increased density. The present invention relates to an ultracapacitor electrode composition, an ultracapacitor electrode manufacturing method using the same, and an ultracapacitor manufactured using the method.

In general, an ultracapacitor is also referred to as an electric double layer capacitor (EDLC) or a supercapacitor, which is a pair having a different sign at an interface between an electrode and a conductor, and an electrolyte solution impregnated therein. The charge layer (electric double layer) of which is generated is used, and deterioration due to repetition of the charge / discharge operation is very small, thus requiring no maintenance. As a result, ultracapacitors are mainly used in the form of backing up of ICs (integrated circuits) of various electric and electronic devices. Recently, their use has been expanded to be widely applied to toys, solar energy storage, and hybrid electric vehicle (HEV) power supplies. have.

Such ultracapacitors generally have two electrodes of an anode and a cathode impregnated with an electrolyte, and a separator made of a porous material for intercalation between the two electrodes to allow only ion conduction and to prevent a short circuit, and leakage of the electrolyte. Gaskets for preventing and short-circuiting, and cases for packaging them.

Ultracapacitor electrodes expressing specific capacitance by physical adsorption and desorption of ions are basically added with an electrically conductive material and a binder in addition to the electrode active material. Carbon black-based conductive materials and binders, which are generally used in the implementation of electrodelization, are used to improve a certain electrical conductivity, enhance the physical properties of electrodes, and improve binding strength between materials. In this case, the binder used is a material having almost no specific capacitance, and when the electrode is manufactured without the binder, the use of the minimum amount is recommended because the surface has a disadvantage that the surface is rough, not smooth, and the density is low and the durability is weak.

In order to improve this problem, in the present invention, by using a small amount of an additive together with a binder not used in an ultracapacitor, the electrode has the advantage of high cell efficiency due to high adhesiveness and high contact with other additives, and thus low resistance. I wanted to make

Republic of Korea Patent Registration No. 10-1635763

The problem to be solved by the present invention is a composition for an ultracapacitor electrode by using a small amount of additives with a binder, good contact with other raw materials, low resistance, increased density and improved durability to exhibit excellent cell efficiency The present invention provides a method of manufacturing an ultracapacitor electrode using the same and an ultracapacitor manufactured using the manufacturing method.

The present invention, 0.1 to 20 parts by weight of a conductive material with respect to 100 parts by weight of the electrode active material, 100 parts by weight of the electrode active material, 1 to 20 parts by weight of the binder relative to 100 parts by weight of the electrode active material, 0.1 to 10 parts by weight of additives based on 100 parts by weight of the electrode active material 100 parts by weight to 100 parts by weight of the dispersion and 100 parts by weight of the electrode active material, wherein the additives include vinyl butyl ether, vinyl ethyl ether, vinyl iso butyl ether, and vinyl iso butyl ether. ), A vinyl methyl ether (Vinyl Methyl ether) and a styrene monomer (Styrene Monomer) provides an ultracapacitor electrode composition comprising at least one material selected from the group consisting of.

The binder may include one or more materials selected from the group consisting of polytetrafluoroethylene (PTFE) and polyvinylidenefluoride (PVDF).

The electrode active material may include at least one material selected from the group consisting of activated carbon having a specific surface area of 1500 to 3000 m ² / g, graphene having a specific surface area of 100 to 1000 m ² / g, carbon nanotubes, and carbon nanofibers. Can be.

In addition, the present invention, 0.1 to 20 parts by weight of a conductive material with respect to 100 parts by weight of the electrode active material, 100 parts by weight of the electrode active material, 1 to 20 parts by weight of the binder relative to 100 parts by weight of the electrode active material, 0.1 additive by weight of 100 parts by weight of the electrode active material Preparing a composition for an ultracapacitor electrode by mixing ~ 10 parts by weight and 100 to 300 parts by weight of the dispersion medium with respect to 100 parts by weight of the electrode active material, and pressing the composition for the ultracapacitor electrode to form an electrode, or the ultracapacitor Forming an electrode composition by coating a metal foil or a current collector in the form of an electrode, or by pressing the ultra-capacitor electrode composition with a roller into a sheet state and pasting a metal foil or a current collector in the form of an electrode and formed in the form of an electrode Drying the result to form an ultracapacitor electrode, the additive being non- 1 type selected from the group consisting of butyl ether, vinyl ethyl ether, vinyl iso butyl ether, vinyl methyl ether, and styrene monomer It provides a method for producing an ultracapacitor electrode comprising the above materials.

The binder may include one or more materials selected from the group consisting of polytetrafluoroethylene (PTFE) and polyvinylidenefluoride (PVDF).

The electrode active material may include at least one material selected from the group consisting of activated carbon having a specific surface area of 1500 to 3000 m ² / g, graphene having a specific surface area of 100 to 1000 m ² / g, carbon nanotubes, and carbon nanofibers. Can be.

In addition, the present invention is disposed between the positive electrode made of the ultracapacitor electrode manufactured by the method, the negative electrode made of the ultracapacitor electrode produced by the method, and disposed between the positive electrode and the negative electrode for preventing a short circuit of the positive electrode and the negative electrode It provides an ultracapacitor comprising a separator, a metal cap in which the positive electrode, the separator and the negative electrode are disposed, and an electrolyte is injected, and a gasket for sealing the metal cap.

In addition, the present invention, a first separator for preventing a short circuit, an anode consisting of an ultracapacitor electrode produced by the method, a second separator for preventing a short circuit between the positive electrode and the negative electrode, ultra manufactured by the method The winding element of which the cathode which consists of a capacitor electrode is laminated | stacked sequentially, and is coiled; A first lead wire connected to the cathode; A second lead wire connected to the anode; A metal cap accommodating the winding element; And a sealing rubber for sealing the metal cap, wherein the winding device provides an ultracapacitor, which is impregnated in an electrolyte in which lithium salt is dissolved.

According to the present invention, by using a small amount of additives with the binder, the contact with other raw materials is good, the resistance is low, the density increase and the durability are improved, so that excellent cell efficiency can be exhibited.

The ultracapacitor manufactured by using the composition for ultracapacitor electrodes of the present invention has high electrode density, shows excellent impedance characteristics, excellent current-to-voltage characteristics (CV characteristics), excellent capacitance characteristics, rate characteristics, and the like.

1 is a cross-sectional view of a coin-type ultracapacitor according to an example.
2 to 5 are views illustrating a wound type ultracapacitor according to an example.
6 is a graph showing the impedance characteristics of the ultracapacitors manufactured according to Example 1 and Comparative Examples.
7 is a graph showing current versus voltage characteristics (CV characteristics) of ultracapacitors manufactured according to Example 1 and Comparative Examples.
8 is a graph showing specific capacitance according to current density of ultracapacitors manufactured according to Example 1 and Comparative Examples.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided to those skilled in the art to fully understand the present invention, and may be modified in various forms, and the scope of the present invention is limited to the embodiments described below. It doesn't happen.

The binder added during the production of the activated carbon electrode is a material having almost no specific capacitance during charging and discharging, and it is recommended to use a minimum amount to realize the physical properties of the electrode and to improve the electrical conductivity. In addition, if the contact with other additives is not smooth, the initial resistance is high and shows a decrease in electrochemical performance, and various studies have been conducted to solve this problem.

The inventors of the present invention have studied a composition for an ultracapacitor electrode which can exhibit good cell efficiency by good contact with other raw materials, low resistance, improved density and durability by using a small amount of an additive together with a binder.

Ultracapacitor electrode composition according to a preferred embodiment of the present invention, the electrode active material, 0.1 to 20 parts by weight of the conductive material with respect to 100 parts by weight of the electrode active material, 1 to 20 parts by weight of the binder relative to 100 parts by weight of the electrode active material, 0.1 to 10 parts by weight of an additive based on 100 parts by weight of the electrode active material and 100 to 300 parts by weight of a dispersion medium based on 100 parts by weight of the electrode active material, wherein the additive includes vinyl butyl ether and vinyl ethyl ether. ), Vinyl iso butyl ether (Vinyl Iso Butyl Ether), vinyl methyl ether (Vinyl Methyl ether) and styrene monomer (Styrene Monomer).

The binder may include one or more materials selected from the group consisting of polytetrafluoroethylene (PTFE) and polyvinylidenefluoride (PVDF).

The electrode active material may include at least one material selected from the group consisting of activated carbon having a specific surface area of 1500 to 3000 m ² / g, graphene having a specific surface area of 100 to 1000 m ² / g, carbon nanotubes, and carbon nanofibers. Can be.

Ultracapacitor electrode manufacturing method according to a preferred embodiment of the present invention, the electrode active material, 0.1 to 20 parts by weight of the conductive material with respect to 100 parts by weight of the electrode active material, 1 to 20 parts by weight of the binder, based on 100 parts by weight of the electrode active material, Mixing 0.1 to 10 parts by weight of the additive with respect to 100 parts by weight of the electrode active material and 100 to 300 parts by weight of the dispersion medium with respect to 100 parts by weight of the electrode active material to prepare a composition for an ultracapacitor electrode, and compressing the ultracapacitor electrode composition. To form an electrode, or the composition for the ultracapacitor electrode is coated on a metal foil or a current collector to form an electrode, or the composition for the ultracapacitor electrode is pushed with a roller into a sheet state and attached to the metal foil or the current collector Forming in the form of an electrode and drying the resultant formed in the form of an electrode Forming an electrode, wherein the additive is vinyl butyl ether, vinyl ethyl ether, vinyl iso butyl ether, vinyl methyl ether, and It includes at least one material selected from the group consisting of styrene monomer (Styrene Monomer).

The binder may include one or more materials selected from the group consisting of polytetrafluoroethylene (PTFE) and polyvinylidenefluoride (PVDF).

The electrode active material may include at least one material selected from the group consisting of activated carbon having a specific surface area of 1500 to 3000 m ² / g, graphene having a specific surface area of 100 to 1000 m ² / g, carbon nanotubes, and carbon nanofibers. Can be.

Ultracapacitor according to a preferred embodiment of the present invention, the anode comprising an ultracapacitor electrode manufactured by the method, the cathode consisting of an ultracapacitor electrode prepared by the method, disposed between the anode and the cathode and the anode and An ultracapacitor including a separator for preventing a short circuit of the cathode, a metal cap in which the anode, the separator and the cathode are disposed therein, and an electrolyte is injected, and a gasket for sealing the metal cap.

According to another preferred embodiment of the present invention, an ultracapacitor includes a first separator for preventing a short circuit, an anode including an ultracapacitor electrode manufactured by the method, a second separator for preventing a short circuit between the anode and the cathode; A winding device comprising a cathode formed of the ultracapacitor electrode manufactured by the above method, sequentially stacked to form a coiled roll; A first lead wire connected to the cathode; A second lead wire connected to the anode; A metal cap accommodating the winding element; And a sealing rubber for sealing the metal cap, wherein the winding device provides an ultracapacitor, which is impregnated in an electrolyte in which lithium salt is dissolved.

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

Ultracapacitor electrode composition according to a preferred embodiment of the present invention, the electrode active material, 0.1 to 20 parts by weight of the conductive material with respect to 100 parts by weight of the electrode active material, 1 to 20 parts by weight of the binder relative to 100 parts by weight of the electrode active material, 0.1 to 10 parts by weight of the additive and 100 to 300 parts by weight of the dispersion medium based on 100 parts by weight of the electrode active material.

The electrode active material may include a porous carbon material such as activated carbon having a specific surface area of 1500 to 3000 m ² / g, graphene having a specific surface area of 100 to 1000 m ² / g, carbon nanotubes, carbon nanofibers, and the like.

The conductive material is not particularly limited as long as it is an electronic conductive material that does not cause chemical change, and examples thereof include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, super-P, carbon fiber, copper, nickel, Metal powders such as aluminum and silver, metal fibers and the like. It is preferable that the said conductive material is contained in the said composition for ultracapacitor electrodes 0.1-20 weight part with respect to 100 weight part of said electrode active materials.

The binder may include one or more materials selected from the group consisting of polytetrafluoroethylene (PTFE) and polyvinylidenefluoride (PVDF). The binder is preferably contained in the composition for the ultracapacitor electrode 1 to 20 parts by weight based on 100 parts by weight of the electrode active material.

The additive is a group consisting of vinyl butyl ether (vinyl butyl ether), vinyl ethyl ether (vinyl ethyl ether), vinyl iso butyl ether (vinyl iso butyl ether), vinyl methyl ether (vinyl methyl ether) and styrene monomer (styrene tyer) At least one substance selected from. The additive does not block the pores of the electrode active material does not lower the electrolyte impregnation, good contact with other additives, low resistance, allows for increased density and improved durability. It is preferable that the additive is contained in the ultracapacitor electrode composition in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the electrode active material.

The dispersion medium is methanol, ethanol, propanol, butanol, butanol, methyl ethyl ketone, methyl iso butyl ketone, toluene and xylene Xylene), distilled water, a mixture thereof, and the like. It is preferable that the said dispersion medium is contained in the said composition for ultracapacitor electrodes 100-300 weight part with respect to 100 weight part of said electrode active materials.

The composition for the ultracapacitor electrode has good contact with other raw materials, low resistance, improved density, and improved durability by using a small amount of an additive together with a binder, thereby exhibiting excellent cell efficiency.

Hereinafter, a method of manufacturing an ultracapacitor electrode using the ultracapacitor electrode composition will be described in more detail.

An electrode active material, a conductive material, a binder, an additive, and a dispersion medium are mixed to prepare a composition for an ultracapacitor electrode.

The composition for the ultracapacitor electrode includes an electrode active material and 0.1 to 20 parts by weight of a conductive material based on 100 parts by weight of the electrode active material, 1 to 20 parts by weight of a binder and 100 parts by weight of the electrode active material based on 100 parts by weight of the electrode active material. 0.1 to 10 parts by weight of the additive and 100 to 300 parts by weight of the dispersion medium per 100 parts by weight of the electrode active material.

The electrode active material may include a porous carbon material such as activated carbon having a specific surface area of 1500 to 3000 m ² / g, graphene having a specific surface area of 100 to 1000 m ² / g, carbon nanotubes, carbon nanofibers, and the like.

The conductive material is not particularly limited as long as it is an electronic conductive material that does not cause chemical change, and examples thereof include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, super-P, carbon fiber, copper, nickel, Metal powders such as aluminum and silver, metal fibers and the like. It is preferable that the said conductive material is contained in the said composition for ultracapacitor electrodes 0.1-20 weight part with respect to 100 weight part of said electrode active materials.

The binder may include one or more materials selected from the group consisting of polytetrafluoroethylene (PTFE) and polyvinylidenefluoride (PVDF). The binder is preferably contained in the composition for the ultracapacitor electrode 1 to 20 parts by weight based on 100 parts by weight of the electrode active material.

The additive is a group consisting of vinyl butyl ether (vinyl butyl ether), vinyl ethyl ether (vinyl ethyl ether), vinyl iso butyl ether (vinyl iso butyl ether), vinyl methyl ether (vinyl methyl ether) and styrene monomer (styrene tyer) At least one substance selected from. The additive does not block the pores of the electrode active material does not lower the electrolyte impregnation, good contact with other additives, low resistance, allows for increased density and improved durability. It is preferable that the additive is contained in the ultracapacitor electrode composition in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the electrode active material.

The dispersion medium is methanol, ethanol, propanol, butanol, butanol, methyl ethyl ketone, methyl iso butyl ketone, toluene and xylene Xylene), distilled water, a mixture thereof, and the like. It is preferable that the said dispersion medium is contained in the said composition for ultracapacitor electrodes 100-300 weight part with respect to 100 weight part of said electrode active materials.

Their uniform mixing (full dispersion) can be difficult, and stirring for a predetermined time (e.g., 10 minutes to 12 hours) using a high speed mixer such as a planetary mixer is suitable for electrode production. The composition for ultracapacitor electrodes can be obtained. High speed mixers, such as planetary mixers, allow for the preparation of uniformly mixed compositions for ultracapacitor electrodes. At this time, it is also possible to induce a uniform dispersion by using an ultrasonic (ultrasonic).

Compress the ultracapacitor electrode composition mixed with an electrode active material, a conductive material, a binder, an additive, and a dispersion medium to form an electrode, or the ultracapacitor electrode composition is coated on a metal foil or a current collector to form an electrode, or The composition for the ultracapacitor electrode is pushed with a roller to form a sheet, attached to a metal foil or a current collector, and formed in the form of an electrode, and the resultant formed in the form of an electrode is dried at a temperature of 100 ° C. to 350 ° C. to form an electrode.

If the example of forming an electrode is demonstrated more concretely, the composition for ultracapacitor electrodes can be crimped | molded using a roll press molding machine. Roll press molding machine aims to improve electrode density and control electrode thickness by rolling, controller to control top and bottom roll and roll thickness and heating temperature, winding to release and wind electrode Contains wealth. As the rolled electrode passes through the roll press, the rolling process proceeds, and the rolled electrode is wound again to complete the electrode. At this time, it is preferable that the pressurization pressure of a roll press is 1-20 ton / cm <2>, and the roll temperature is 0-150 degreeC. The composition for the ultracapacitor electrode, which has undergone the above press pressing process, is subjected to a drying process. The drying process is carried out at a temperature of 100 ° C to 350 ° C, preferably 150 ° C to 300 ° C. At this time, when the drying temperature is less than 100 ℃ is not preferable because the evaporation of the dispersion medium is difficult, and when the high temperature drying over 350 ℃ may occur oxidation of the conductive material is not preferable. Therefore, it is preferable that drying temperature is 100 degreeC or more and does not exceed 350 degreeC. And the drying process is preferably carried out for about 10 minutes to 12 hours at the above temperature. Such a drying process binds the electrode active material and the conductive material particles to improve the strength of the electrode.

In another example of forming an electrode, the ultracapacitor electrode composition may include a metal foil or an etching method such as a titanium foil, an aluminum foil, an etched aluminum foil, or the like. It may be coated on a current collector such as an aluminum current collector, or the ultracapacitor electrode composition may be pushed with a roller into a sheet state (rubber type) and attached to a metal foil or a current collector to form a positive electrode or a negative electrode. The etched aluminum foil means that the aluminum foil is etched in an uneven shape, and the etched aluminum current collector means that the aluminum current collector is etched in a request shape. The drying process is performed on the shape of the positive electrode or the negative electrode which has been subjected to the above process. The drying process is carried out at a temperature of 100 ° C to 350 ° C, preferably 150 ° C to 300 ° C. At this time, when the drying temperature is less than 100 ℃ is not preferable because the evaporation of the dispersion medium is difficult, and when the high temperature drying over 350 ℃ may occur oxidation of the conductive material is not preferable. Therefore, it is preferable that drying temperature is 100 degreeC or more and does not exceed 350 degreeC. And the drying process is preferably carried out for about 10 minutes to 6 hours at the above temperature. Through the drying process to bind the electrode active material and the conductive material particles to improve the strength of the electrode.

The ultracapacitor electrode manufactured as described above may be usefully applied to a small coin-type ultracapacitor as shown in FIG. 1, a wound ultracapacitor as shown in FIGS. 2 to 5, and the like.

1 is a state diagram of use of an ultracapacitor electrode according to the present invention, showing a cross-sectional view of a coin-type ultracapacitor to which the ultracapacitor electrode is applied. In FIG. 1, reference numeral 190 denotes a metal cap as a conductor, reference numeral 160 denotes a separator of a porous material for preventing insulation and short circuit between the anode 120 and the cathode 110, and reference numeral 192 denotes a leakage of an electrolyte solution. To prevent insulation and short circuit. At this time, the positive electrode 120 and the negative electrode 110 are firmly fixed by the metal cap 190 and the adhesive.

The coin-type ultracapacitor includes a positive electrode 120 made of the above-mentioned ultracapacitor electrode, a negative electrode 110 made of the above-mentioned ultracapacitor electrode, and disposed between the positive electrode 120 and the negative electrode 110. After the separator 160 is disposed in the metal cap 190 to prevent a short circuit between the cathode 120 and the cathode 120, the electrolyte solution in which the electrolyte is dissolved is injected between the anode 120 and the cathode 110. It may be manufactured by sealing with a gasket 192.

The separator may be 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 the like. If the separator is generally used in the field is not particularly limited.

Meanwhile, the electrolyte filled in the ultracapacitor is TEABF ₄ (tetraethylammonium tetrafluoborate) and TEMABF ₄ (at least one solvent selected from propylene carbonate (PC), acetonitrile (AN; acetonitrile) and sulfolane (SL)). triethylmethylammonium tetrafluoborate) can be used that is dissolved at least one salt selected from. In addition, the electrolyte may include one or more ionic liquids selected from EMIBF ₄ (1-ethyl-3-methyl imidazolium tetrafluoborate) and EMITFSI (1-ethyl-3-methyl imidazolium bis (trifluoromethane sulfonyl) imide). .

2 to 5 are diagrams illustrating a state of use of the ultracapacitor electrode according to another example, and showing a wound type ultracapacitor to which the ultracapacitor electrode is applied. A method of manufacturing a wound ultracapacitor will be described in detail with reference to FIGS. 2 to 5.

As shown in FIG. 2, lead wires 130 and 140 are attached to the anode 120 and the cathode 110 formed of the ultracapacitor electrode described above.

As shown in FIG. 3, the first separator 150, the anode 120, the second separator 160, and the working electrode (the cathode 110) are stacked, coiled, and rolled to form a roll. After the fabrication of the winding device 175, the roll (roll) around the roll (rolling) with an adhesive tape 170 to maintain the roll shape.

The second separator 160 provided between the anode 120 and the cathode 110 serves to prevent a short circuit between the anode 120 and the cathode 110. The first and second separators 150 and 160 are polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, polyacrylonitrile porous separator, poly (vinylidene fluoride) hexafluoropropane copolymer porous separator, cellulose porous separator, kraft paper Or if the separator is generally used in the field of batteries and capacitors, such as rayon fibers are not particularly limited.

As shown in FIG. 4, a sealing rubber 180 is mounted on a roll-shaped product, and a sealing rubber 180 is mounted on a metal cap (eg, an aluminum case) 190.

The electrolyte is injected and sealed so that the roll-shaped winding element 175 (the anode 120 and the cathode 110) is impregnated. The electrolyte solution is selected from propylene carbonate (PC; propylene carbonate), acetonitrile (AN; acetonitrile), and sulfolane (SL; sulfolane) in at least one solvent selected from TEABF ₄ (tetraethylammonium tetrafluoborate) and TEMABF ₄ (triethylmethylammonium tetrafluoborate). It can use what melt | dissolved more than a kind of salt. In addition, the electrolyte may include one or more ionic liquids selected from EMIBF ₄ (1-ethyl-3-methyl imidazolium tetrafluoborate) and EMITFSI (1-ethyl-3-methyl imidazolium bis (trifluoromethane sulfonyl) imide). .

The winding type ultracapacitor manufactured as described above is schematically illustrated in FIG. 5.

In the following, examples according to the present invention are presented in detail, and the present invention is not limited to the following examples.

<Example 1>

20 mL of ethanol was prepared as a solvent when preparing the electrode, and an electrode active material, a conductive material, a binder, and vinyl butyl ether were prepared in a weight ratio of 90: 5: 4: 1. More specifically, 9 g of activated carbon as an electrode active material, 0.5 g of carbon black as a conductive material, 0.4 g of polytetrafluoroethylene (PTFE) as a binder, and 0.1 g of vinyl butyl ether were prepared. Raw materials other than polytetrafluoroethylene (PTFE) and vinyl butyl ether were placed in a stirring vessel and stirred at 2000 rpm for about 20 minutes using an ARM-310 Planetary centrifugal mixer. After the stirring was completed, polytetrafluoroethylene (PTFE) and vinyl butyl ether were added, and then stirred at 2000 rpm for 20 minutes to prepare a composition for an ultracapacitor electrode.

The composition for ultracapacitor electrodes was rolled to a thickness of 200 μm using a roll press equipment.

The rolled product was dried in a drier for at least 12 hours to prepare a rubber type electrode.

The electrode thus prepared was punched out to a diameter of 12 mm and used as an ultracapacitor electrode.

The ultracapacitor electrode was assembled into a full cell with a coin type 2032 cell to form an ultracapacitor. At this time, the membrane was used TF4035 of NKK, the electrolyte was dissolved in 1M TEABF ₄ (tetraethylammonium tetrafluoborate) in ACN (acetonitrile).

Comparative Example

20 mL of ethanol was prepared as a solvent when preparing the electrode, and an electrode active material, a conductive material, and a binder were prepared in a weight ratio of 90: 5: 4. More specifically, 9g of activated carbon as an electrode active material, 0.5g of carbon black as a conductive material, and 0.4g of polytetrafluoroethylene (PTFE) as a binder were prepared. Raw materials other than polytetrafluoroethylene (PTFE) were placed in a stirring vessel and stirred at 2000 rpm for about 20 minutes using an ARM-310 Planetary centrifugal mixer. After the stirring was completed, polytetrafluoroethylene (PTFE) was added and then stirred at 2000 rpm for 20 minutes to prepare a composition for an ultracapacitor electrode.

The composition for ultracapacitor electrodes was rolled to a thickness of 200 μm using a roll press equipment.

The rolled product was dried in a drier for at least 12 hours to prepare a rubber type electrode.

The electrode thus prepared was punched out to a diameter of 12 mm and used as an ultracapacitor electrode.

The ultracapacitor electrode was assembled into a full cell with a coin type 2032 cell to form an ultracapacitor. At this time, the membrane was used TF4035 of NKK, the electrolyte was dissolved in 1M TEABF ₄ (tetraethylammonium tetrafluoborate) in ACN (acetonitrile).

Table 1 below shows the characteristics of the ultracapacitor electrodes prepared according to Example 1 and Comparative Examples.

division Comparative example Example 1 Thickness (㎛) 200 200 Volume (cc) 0.0226 0.0224 Weight of electrode (g) 0.0129 0.0151 Electrode Density (g / cc) 0.57 0.67

As shown in Table 1, it was confirmed that the density of the ultracapacitor electrode prepared according to Example 1 is higher than the density of the ultracapacitor electrode prepared according to the comparative example.

6 shows the impedance characteristics of the ultracapacitors manufactured according to Example 1 and Comparative Examples.

Referring to FIG. 6, the impedance characteristics of the ultracapacitor manufactured according to Example 1 were superior to the impedance characteristics of the ultracapacitor manufactured according to the comparative example.

7 shows the current versus voltage characteristics (CV characteristics) of the ultracapacitors prepared according to Example 1 and Comparative Examples.

Referring to FIG. 7, the CV characteristics of the ultracapacitors prepared according to Example 1 were superior to those of the ultracapacitors manufactured according to the comparative example.

Table 2 and Figure 8 below shows the specific capacitance according to the current density of the ultracapacitor prepared according to Example 1 and Comparative Example.

Current density
(mA / ㎠) Specific capacitance (F / cc) Comparative example Example One 14.6 15.5 2 14.3 15.4 5 13.6 15.2 10 13.1 14.9 20 11.9 14.5

Referring to Table 1 and FIG. 8, the specific capacitance according to the current density of the ultracapacitor manufactured according to Example 1 was superior to the specific capacitance according to the current density of the ultracapacitor manufactured according to the comparative example.

As mentioned above, although the preferred embodiment of this invention was described in detail, this invention is not limited to the said embodiment, A various deformation | transformation by a person of ordinary skill in the art within the scope of the technical idea of this invention is carried out. 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 (8)

Electrode active materials;
0.1-20 parts by weight of conductive material based on 100 parts by weight of the electrode active material;
1 to 20 parts by weight of the binder with respect to 100 parts by weight of the electrode active material;
0.1 to 10 parts by weight of an additive based on 100 parts by weight of the electrode active material; And
100 to 300 parts by weight of the dispersion medium per 100 parts by weight of the electrode active material,
The additive includes a styrene monomer (Styrene Monomer),
The electrode active material is an ultracapacitor electrode composition, characterized in that it comprises at least one material selected from the group consisting of graphene, carbon nanotubes and carbon nanofibers having a specific surface area of 100 ~ 1000 m ² / g.
The composition of claim 1, wherein the binder comprises at least one material selected from the group consisting of polytetrafluoroethylene and polyvinylidenefluoride.
delete 0.1-20 parts by weight of conductive material based on 100 parts by weight of electrode active material, 100 parts by weight of electrode active material, 1 to 20 parts by weight of binder based on 100 parts by weight of electrode active material, 0.1 to 10 parts by weight of additive based on 100 parts by weight of electrode active material Preparing a composition for an ultracapacitor electrode by mixing 100 to 300 parts by weight of the dispersion medium with respect to 100 parts by weight of the electrode active material;
The ultracapacitor electrode composition is compressed to form an electrode, or the ultracapacitor electrode composition is coated on a metal foil or a current collector to form an electrode, or the ultracapacitor electrode composition is pushed with a roller to form a sheet. Attaching to a metal foil or a current collector to form an electrode; And
Drying the resultant formed in the form of an electrode to form an ultracapacitor electrode,
The additive includes a styrene monomer (Styrene Monomer),
The electrode active material manufacturing method of the ultracapacitor electrode, characterized in that it comprises at least one material selected from the group consisting of graphene, carbon nanotubes and carbon nanofibers having a specific surface area of 100 ~ 1000 m ² / g.
The method of claim 4, wherein the binder comprises at least one material selected from the group consisting of polytetrafluoroethylene and polyvinylidenefluoride. 6.
delete An anode comprising an ultracapacitor electrode produced by the method of claim 4;
A negative electrode consisting of an ultracapacitor electrode produced by the method of claim 4;
A separator disposed between the positive electrode and the negative electrode to prevent a short circuit between the positive electrode and the negative electrode;
A metal cap in which the anode, the separator, and the cathode are disposed therein and an electrolyte is injected; And
Ultracapacitor comprising a gasket for sealing the metal cap.
A first separator for preventing a short circuit, an anode comprising an ultracapacitor electrode manufactured by the method of claim 4, a second separator for preventing a short circuit between the anode and the cathode, and a method according to claim 4 A cathode comprising an ultracapacitor electrode, which is sequentially stacked to form a coiled roll;
A first lead wire connected to the cathode;
A second lead wire connected to the anode;
A metal cap accommodating the winding element; And
A sealing rubber for sealing the metal cap,
The winding element is an ultracapacitor, which is impregnated in an electrolyte solution in which lithium salt is dissolved.

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