KR102188242B1 - Composite for supercapacitor electrode, manufacturing method of supercapacitor electrode using the composite, and supercapacitor manufactured by the method - Google Patents

Abstract

The present invention relates to a composition for a supercapacitor electrode, a manufacturing method of a supercapacitor electrode using the same, and a supercapacitor manufactured by using the manufacturing method. The composition for a supercapacitor electrode comprises: an electrode active material; 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 fluorine-containing binder based on 100 parts by weight of the electrode active material; 0.01 to 2 parts by weight of an additive based on 100 parts by weight of the electrode active material; 100 to 300 parts by weight of a dispersion medium based on 100 parts by weight of the electrode active material. The additive contains 2-dimethylaminoethyl methacrylate (2-(dimethylamino)ethyl methacrylate). According to the present invention, the moldability can be improved, the durability of the electrode can be improved, and the electrode density can be improved.

Description

A composition for a supercapacitor electrode that can improve electrode density, a method of manufacturing a supercapacitor electrode using the same, and a supercapacitor manufactured using the manufacturing method (Composite for supercapacitor electrode, manufacturing method of supercapacitor electrode using the composite, and supercapacitor manufactured) by the method}

The present invention relates to a composition for a supercapacitor electrode, a method of manufacturing a supercapacitor electrode, and a supercapacitor, and in more detail, it is possible to improve moldability, improve durability of the electrode, and improve electrode density. It relates to a composition for a supercapacitor electrode, a method of manufacturing a supercapacitor electrode, and a supercapacitor.

Among next-generation energy storage devices, supercapacitors are in the spotlight as next-generation energy storage devices due to their fast charging/discharging speed, high stability, and eco-friendly characteristics. A general supercapacitor is composed of a porous electrode, a current collector, a separator, and an electrolyte.

Supercapacitors are also referred to as Electric Double Layer Capacitors (EDLC) and Ultra-capacitors, and this is a pair of charge layers with different codes at the interface between the electrode and the conductor and the electrolyte impregnated therein ( It is a device that does not require maintenance due to very low deterioration due to repetition of charging/discharging operation by using the generated electric double layer). Accordingly, supercapacitors are mainly used in the form of backing up ICs (integrated circuits) of various electric and electronic devices, and their use has been expanded in recent years and has been widely applied to toys, solar energy storage, and HEV (hybrid electric vehicle) power supplies. have.

Such supercapacitors generally include two electrodes, a positive electrode and a negative electrode impregnated with an electrolyte, and a separator made of a porous material for insulating and short-circuit prevention, and an electrolyte that is interposed between these two electrodes to enable only ion conduction. It has a unit cell composed of a gasket to prevent leakage of the product, insulation and short circuit, and a metal cap as a conductor that wraps them. And it is completed by stacking one or more unit cells (usually 2-6 in the case of coin type) in series and combining the two terminals of the positive and negative electrodes.

The performance of a supercapacitor is determined by the electrode active material and electrolyte, and in particular, the main performance such as storage capacity is mostly determined by the electrode active material. Activated carbon is mainly used as such an electrode active material, and the reserve capacity is known to be up to 19.3 F/cc based on electrodes of commercial products. In general, activated carbon used as an electrode active material for supercapacitors is activated carbon with a high specific surface area of 1500 m 2 /g or more.

However, as the application field of supercapacitors expands, higher specific storage capacity and energy density are required, and thus, development of supercapacitors that exhibit higher storage capacity is required.

Korean Patent Registration No. 10-1137719

The problem to be solved by the present invention is to provide a composition for a supercapacitor electrode, a method of manufacturing a supercapacitor electrode, and a supercapacitor capable of improving moldability, improving durability of the electrode, and improving electrode density. have.

The present invention, an electrode active material; 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 fluorine-containing binder based on 100 parts by weight of the electrode active material, and 0.01 to 2 parts by weight of an additive based on 100 parts by weight of the electrode active material , A composition for a supercapacitor electrode comprising 100 to 300 parts by weight of a dispersion medium based on 100 parts by weight of the electrode active material, and wherein the additive comprises 2-(dimethylamino)ethyl methacrylate. Provides.

The composition for a supercapacitor electrode further comprises 0.01 to 2 parts by weight of 2-[(3-acrylamidopropyl dimethylammonio] acetate) with respect to 100 parts by weight of the electrode active material (CBAA; 2-[(3-acrylamidopropyl) dimethylammonio] acetate) Can include.

The fluorine-containing binder may include polytetrafluoroethylene (PTFE).

The electrode active material is made of activated carbon with a specific surface area of 1500 to 3000 m ² /g, graphene with a specific surface area of 100 to 1000 m ² /g, carbon nanotubes (CNTs), and carbon nanofibers. It may contain one or more materials selected from the group.

In addition, the present invention provides an electrode active material, 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 fluorine-containing binder based on 100 parts by weight of the electrode active material, and 100 parts by weight of the electrode active material. Preparing a composition for a supercapacitor electrode by mixing 0.01 to 2 parts by weight of an additive and 100 to 300 parts by weight of a dispersion medium with respect to 100 parts by weight of the electrode active material, and forming an electrode by pressing the composition for a supercapacitor electrode, or Coating the composition for a supercapacitor electrode on a metal foil or a current collector to form an electrode, or forming a sheet by pushing the composition for a supercapacitor electrode with a roller and attaching it to a metal foil or a current collector to form an electrode and the electrode form A method of manufacturing a supercapacitor electrode, comprising the step of forming a supercapacitor electrode by drying the resulting product, wherein the additive comprises 2-(dimethylamino)ethyl methacrylate. Provides.

The composition for a supercapacitor electrode further comprises 0.01 to 2 parts by weight of 2-[(3-acrylamidopropyl dimethylammonio] acetate) with respect to 100 parts by weight of the electrode active material (CBAA; 2-[(3-acrylamidopropyl) dimethylammonio] acetate) Can include.

The fluorine-containing binder may include polytetrafluoroethylene (PTFE).

The electrode active material is made of activated carbon with a specific surface area of 1500 to 3000 m ² /g, graphene with a specific surface area of 100 to 1000 m ² /g, carbon nanotubes (CNTs), and carbon nanofibers. It may contain one or more materials selected from the group.

In addition, the present invention, the anode made of a supercapacitor electrode manufactured by the above method; A cathode made of a supercapacitor electrode manufactured by the above method; A separator disposed between the anode and the cathode to prevent a short circuit between the anode and the cathode; A metal cap in which the anode, the separator, and the cathode are disposed and an electrolyte is injected; And it provides a supercapacitor including a gasket for sealing the metal cap.

In addition, the present invention provides a first separator for preventing a short circuit, an anode comprising a supercapacitor electrode manufactured by the above method, a second separator for preventing a short circuit between the anode and the cathode, and a supercapacitor manufactured by the method. A winding element in which a cathode made of a capacitor electrode is sequentially stacked to form a coiled roll; A first lead wire connected to the negative electrode; A second lead wire connected to the positive electrode; A metal cap accommodating the winding element; And a sealing rubber for sealing the metal cap, wherein the winding element is impregnated with an electrolyte in which a lithium salt is dissolved.

According to the present invention, the moldability can be improved, the durability of the electrode can be improved, and the electrode density can be improved. By using a small amount of additives together with a binder, the contact with other raw materials is good, resistance is low, density increase and durability are improved, thereby enabling excellent cell efficiency.

A supercapacitor manufactured using the composition for a supercapacitor electrode of the present invention has a high electrode density, exhibits high capacity characteristics as the energy density increases, and exhibits excellent specific capacity characteristics.

1 is a cross-sectional view of a coin-type supercapacitor according to an example.
2 to 5 are views showing a wound-type supercapacitor according to an example.
6 is a diagram showing electrochemical analysis results of a supercapacitor manufactured according to Example 1 and a supercapacitor manufactured according to a comparative example.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided so that the present invention may be sufficiently understood by those of ordinary skill in the art, and may be modified in various other forms, and the scope of the present invention is limited to the embodiments described below. It does not become.

In the detailed description of the invention or in the claims, when any one component "includes" another component, it is not construed as being limited to consisting of only the component unless otherwise stated, and other components are further included. It should be understood that it may contain.

The composition for a supercapacitor electrode according to a preferred embodiment of the present invention includes an electrode active material; 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 fluorine-containing binder based on 100 parts by weight of the electrode active material, and 0.01 to 2 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, and the additive includes 2-(dimethylamino)ethyl methacrylate.

The composition for a supercapacitor electrode further comprises 0.01 to 2 parts by weight of 2-[(3-acrylamidopropyl dimethylammonio] acetate) with respect to 100 parts by weight of the electrode active material (CBAA; 2-[(3-acrylamidopropyl) dimethylammonio] acetate) Can include.

The fluorine-containing binder may include polytetrafluoroethylene (PTFE).

The electrode active material is made of activated carbon with a specific surface area of 1500 to 3000 m ² /g, graphene with a specific surface area of 100 to 1000 m ² /g, carbon nanotubes (CNTs), and carbon nanofibers. It may contain one or more materials selected from the group.

A method of manufacturing a supercapacitor electrode according to a preferred embodiment of the present invention includes an electrode active material, 0.1 to 20 parts by weight of a conductive material based on 100 parts by weight of the electrode active material, and 1 to 20 parts by weight of a fluorine-containing binder based on 100 parts by weight of the electrode active material. Parts, preparing a composition for a supercapacitor electrode by mixing 0.01 to 2 parts by weight of an additive and 100 to 300 parts by weight of a dispersion medium based on 100 parts by weight of the electrode active material, and the composition for a supercapacitor electrode Is formed in the form of an electrode by pressing the supercapacitor electrode, or the composition for supercapacitor electrode is coated on a metal foil or a current collector to form an electrode, or the composition for a supercapacitor electrode is pushed with a roller to form a sheet and applied to the metal foil or current collector. And forming a supercapacitor electrode by attaching to form an electrode and drying the resulting product in the form of an electrode, and the additive includes 2-(dimethylamino)ethyl methacrylate. .

The composition for a supercapacitor electrode further comprises 0.01 to 2 parts by weight of 2-[(3-acrylamidopropyl dimethylammonio] acetate) with respect to 100 parts by weight of the electrode active material (CBAA; 2-[(3-acrylamidopropyl) dimethylammonio] acetate) The 2-[(3-acrylamidopropyl dimethylammonio acetate) enhances the binding force to the current collector, improves the impregnation property of the electrolyte, and enables the improvement of electrode density.

The fluorine-containing binder may include polytetrafluoroethylene (PTFE).

The electrode active material is made of activated carbon with a specific surface area of 1500 to 3000 m ² /g, graphene with a specific surface area of 100 to 1000 m ² /g, carbon nanotubes (CNTs), and carbon nanofibers. It may contain one or more materials selected from the group.

A supercapacitor according to a preferred embodiment of the present invention includes an anode made of a supercapacitor electrode manufactured by the above method; A cathode made of a supercapacitor electrode manufactured by the above method; A separator disposed between the anode and the cathode to prevent a short circuit between the anode and the cathode; A metal cap in which the anode, the separator, and the cathode are disposed and an electrolyte is injected; And a gasket for sealing the metal cap.

A supercapacitor according to another preferred embodiment of the present invention includes a first separator for preventing a short circuit, an anode comprising a supercapacitor electrode manufactured by the above method, a second separator for preventing a short circuit between the anode and the cathode, and , A winding element in which a cathode made of a supercapacitor electrode manufactured by the above method is sequentially stacked to form 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 accommodating the winding element; And a sealing rubber for sealing the metal cap, wherein the winding element is impregnated in an electrolyte solution in which a lithium salt is dissolved.

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

It is recommended to use a minimum amount of a binder added in the manufacture of an existing activated carbon electrode to improve electrical conductivity. In addition, if the contact with other additives is not smooth, the initial resistance is high and the electrochemical performance is deteriorated. Therefore, several studies are being conducted to solve this problem.

The inventors of the present invention have studied a composition for a supercapacitor electrode that can exhibit excellent cell efficiency by improving contact with other raw materials, low resistance, increased electrode density, and improved durability by using a small amount of additives with a binder. .

The composition for a supercapacitor electrode according to a preferred embodiment of the present invention includes an electrode active material; 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 fluorine-containing binder based on 100 parts by weight of the electrode active material, and 0.01 to 2 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, and the additive includes 2-(dimethylamino)ethyl methacrylate.

The electrode active material is made of activated carbon with a specific surface area of 1500 to 3000 m ² /g, graphene with a specific surface area of 100 to 1000 m ² /g, carbon nanotubes (CNTs), and carbon nanofibers. It may contain one or more materials selected from the group.

The fluorine-containing binder may include polytetrafluoroethylene (PTFE). The fluorine-containing binder is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the electrode active material in the composition for a supercapacitor electrode.

The conductive material is not particularly limited as long as it is an electronic conductive material that does not cause chemical changes, and examples thereof include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, Super-P, carbon fiber, copper, nickel, Metal powder or metal fibers such as aluminum and silver may be used. The conductive material is preferably contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the electrode active material in the composition for a supercapacitor electrode.

The dispersion medium is methanol, ethanol, propanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, toluene, and xylene ( Xylene), distilled water, and mixtures thereof. The dispersion medium is preferably contained in the composition for a supercapacitor electrode in an amount of 100 to 300 parts by weight based on 100 parts by weight of the electrode active material.

The additive includes 2-(dimethylamino)ethyl methacrylate. The 2-dimethylaminoethyl methacrylate improves the moldability, improves the durability of the electrode, and makes it possible to improve the electrode density. The additive is preferably contained in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the electrode active material in the composition for a supercapacitor electrode. The structural formula of 2-dimethylaminoethyl methacrylate is shown below.

[Structural Formula 1]

The composition for a supercapacitor electrode further comprises 0.01 to 2 parts by weight of 2-[(3-acrylamidopropyl dimethylammonio] acetate) with respect to 100 parts by weight of the electrode active material (CBAA; 2-[(3-acrylamidopropyl) dimethylammonio] acetate) The 2-[(3-acrylamidopropyl dimethylammonio acetate) enhances the binding force to the current collector, improves the impregnation property of the electrolyte, and enables the improvement of electrode density.

The structural formula of 2-[(3-acrylamidopropyl dimethylammonio acetate) is shown below.

[Structural Formula 2]

The composition for a supercapacitor electrode has good contact with other raw materials, low resistance, increased electrode density, and improved durability by using a small amount of additives together with a binder, thereby enabling excellent cell efficiency.

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

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

The composition for a supercapacitor electrode comprises an electrode active material, 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 based on 100 parts by weight of the electrode active material, and 100 parts by weight of the electrode active material. It includes 0.01 to 2 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 changes, and examples thereof include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, Super-P, carbon fiber, copper, nickel, Metal powder or metal fibers such as aluminum and silver may be used. The conductive material is preferably contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the electrode active material in the composition for a supercapacitor electrode.

The fluorine-containing binder may include polytetrafluoroethylene (PTFE). The fluorine-containing binder is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the electrode active material in the composition for a supercapacitor electrode.

The dispersion medium is methanol, ethanol, propanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, toluene, and xylene ( Xylene), distilled water, and mixtures thereof. The dispersion medium is preferably contained in the composition for a supercapacitor electrode in an amount of 100 to 300 parts by weight based on 100 parts by weight of the electrode active material.

The additive includes 2-(dimethylamino)ethyl methacrylate. The 2-dimethylaminoethyl methacrylate improves the moldability, improves the durability of the electrode, and makes it possible to improve the electrode density. The additive is preferably contained in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the electrode active material in the composition for a supercapacitor electrode.

The composition for a supercapacitor electrode further comprises 0.01 to 2 parts by weight of 2-[(3-acrylamidopropyl dimethylammonio] acetate) with respect to 100 parts by weight of the electrode active material (CBAA; 2-[(3-acrylamidopropyl) dimethylammonio] acetate) The 2-[(3-acrylamidopropyl dimethylammonio acetate) improves moldability, improves the durability of the electrode, and enables the improvement of electrode density.

It may be difficult to uniformly mix (completely disperse) these, but if a high-speed mixer such as a planetary mixer is used and agitated for a predetermined period of time (for example, 10 minutes to 12 hours), it is suitable for electrode manufacturing. A composition for a supercapacitor electrode can be obtained. A high-speed mixer such as a planetary mixer enables the preparation of a uniformly mixed composition for supercapacitor electrodes. At this time, it is also possible to induce uniform dispersion by using ultrasonic waves.

A composition for a supercapacitor electrode, which is a mixture of an electrode active material, a conductive material, a fluorine-containing binder, an additive, and a dispersion medium, is pressed to form an electrode, or the composition for a supercapacitor electrode is coated on a metal foil or a current collector to form an electrode. , The supercapacitor electrode composition is pushed with a roller to form a sheet, and attached to a metal foil or a current collector to form an electrode, and the resultant formed in the electrode form is dried to form an electrode.

When an example of forming an electrode is described in more detail, the composition for a supercapacitor electrode may be pressed and molded using a roll press molding machine. The roll press forming machine is aimed at improving electrode density and controlling the thickness of the electrode through rolling, a controller that can control the thickness and heating temperature of the rolls and rolls at the top and bottom, and a winding that can unwind and wind the electrode. Includes wealth. As the rolled electrode passes through the roll press, the rolling process proceeds, and it is wound in a rolled state to complete the electrode. At this time, the pressing pressure of the roll press is preferably 1 to 20 ton/cm 2 and the temperature of the roll is 0 to 150°C. The composition for a supercapacitor electrode that has undergone the press compression process as described above 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. In this case, when the drying temperature is less than 100°C, evaporation of the dispersion medium is difficult, which is not preferable, and when drying at a high temperature exceeding 350°C, oxidation of the conductive material may occur, which is not preferable. Therefore, it is preferable that the drying temperature is not less than 100°C and not more than 350°C. And the drying process is preferably carried out for about 10 minutes to 12 hours at the same temperature as above. This drying process improves the strength of the electrode by binding the electrode active material and the conductive material particles.

In addition, looking at another example of forming an electrode, the composition for the supercapacitor electrode is used as a metal foil such as a titanium foil, an aluminum foil, or an etching aluminum foil, or etching. It may be coated on a current collector such as an aluminum current collector, or the composition for a supercapacitor electrode may be pushed with a roller to form a sheet (rubber type) and attached to a metal foil or current collector to form a positive or negative electrode shape. 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 requested shape. A drying process is performed on the shape of the anode or cathode that has undergone the above process. The drying process is carried out at a temperature of 100°C to 350°C, preferably 150°C to 300°C. In this case, when the drying temperature is less than 100°C, evaporation of the dispersion medium is difficult, which is not preferable, and when drying at a high temperature exceeding 350°C, oxidation of the conductive material may occur, which is not preferable. Therefore, it is preferable that the drying temperature is not less than 100°C and not more than 350°C. And the drying process is preferably carried out for about 10 minutes to 6 hours at the same temperature as above. Through the drying process, the electrode active material and the conductive material particles are bound to improve the strength of the electrode.

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

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

The coin-type supercapacitor is disposed between the positive electrode 120 made of the above-described supercapacitor electrode, the negative electrode 110 made of the above-described supercapacitor electrode, and the positive electrode 120 and the negative electrode 110, and the positive electrode 120 A separator 160 for preventing a short circuit between the anode and cathode 120 is disposed in the metal cap 190, and an electrolyte solution in which the electrolyte is dissolved between the anode 120 and the cathode 110 is injected, It can be manufactured by sealing with a gasket 192.

The separator is 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 rayon fiber, etc. It is not particularly limited as long as it is a separator generally used in the field.

On the other hand, the electrolyte to be filled in the supercapacitor is TEABF ₄ (tetraethylammonium tetrafluoborate) and TEMABF ₄ (tetraethylammonium tetrafluoborate) and TEMABF ₄ ( triethylmethylammonium tetrafluoborate) in which one or more salts selected from among them are dissolved may be used. 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 a supercapacitor electrode according to another example, and are views illustrating a wound-type supercapacitor to which the supercapacitor electrode is applied. A method of manufacturing a wound-type supercapacitor 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 cathode 110 made of the above-described supercapacitor electrode, respectively.

As shown in FIG. 3, a first separator 150, an anode 120, a second separator 160, and a working electrode (cathode 110) are stacked, and coiled to form a roll. After being manufactured with the winding element 175 of, the roll shape is maintained by winding it with an adhesive tape 170 or the like around the roll.

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 non-woven fabric, polypropylene non-woven fabric, polyester non-woven fabric, polyacrylonitrile porous separator, poly(vinylidene fluoride) hexafluoropropane copolymer porous separator, cellulose porous separator, and kraft paper. Or, if it is a separator generally used in the field of batteries and capacitors such as rayon fiber, there is no particular limitation.

As shown in FIG. 4, a sealing rubber 180 is mounted on the resultant in the form of a roll, and a metal cap (eg, an aluminum case) 190 is inserted.

The electrolyte is injected and sealed so that the roll-shaped winding element 175 (positive electrode 120 and negative electrode 110) is impregnated. The electrolyte is 1 selected from TEABF ₄ (tetraethylammonium tetrafluoborate) and TEMABF ₄ (triethylmethylammonium tetrafluoborate) in one or more solvents selected from propylene carbonate (PC; propylene carbonate), acetonitrile (AN; acetonitrile) and sulfolane (SL). It is possible to use those in which more than one species are dissolved. 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 wound-type supercapacitor manufactured as described above is schematically shown in FIG. 5.

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

<Example 1>

0.05 g of 2-(dimethylamino)ethyl methacrylate (hereinafter referred to as'DMAEMA') was added to 5 g of a dispersion medium in which ethanol and water were mixed in a volume ratio of 1:1, followed by stirring to form a DMAEMA solution. .

To the 2-dimethylaminoethyl methacrylate solution, 0.45 g of polytetrafluoroethylene (PTFE) as a fluorine-containing binder and 15 g of distilled water as a dispersion medium were added and stirred at a speed of 2000 rpm using a high-speed mixer to DMAEMA-binder. A mixed solution was formed.

9g of commercial activated carbon YP50F (Kurary, Japan) as an electrode active material and 0.05g of super-P (super-P) as a conductive material were added to the DMAEMA-binder mixed solution, and then a paste-like electrode composition was prepared using a high-speed mixer. .

The composition for electrodes in a kneaded state was molded in a roll press molding machine until the surface became smooth to form a sheet of the composition for electrodes. The roll press molding machine is provided including an upper roll and a lower roll, and is formed by passing the electrode composition between the upper and lower rolls. The result of passing between the upper roll and the lower roll was folded in half, and the process of passing between the upper and lower rolls was repeated 15 times to obtain a sheet of the composition for electrodes having a smooth surface. Through rolling of the roll press forming machine, the electrode density can be improved and the thickness of the electrode can be controlled. The pressurization pressure applied to the electrode composition was about 10 ton/cm 2, and the heating temperature was about 60°C.

The electrode composition sheet formed using a roll press molding machine was punched into a size of 12 mm in diameter. The resulting product formed by punching was dried in a vacuum dryer. The drying was performed at a temperature of 150° C. for 24 hours.

The electrode sheet thus prepared was used as a supercapacitor electrode.

Using the prepared supercapacitor electrode as an anode and a cathode, a coin cell type supercapacitor having a diameter of 20 mm and a height of 3.2 mm was manufactured. At this time, in manufacturing the coin cell, an electrolyte containing 1M of TEABF ₄ in a propylene carbonate (PC) solvent was used, and TF4035 (manufactured by NKK, Japan) was used as the separator.

A comparative example is presented so that the characteristics of Example 1 can be more easily grasped, and the comparative examples below are presented merely to aid understanding and are not prior art of the present invention.

<Comparative Example>

0.45 g of polytetrafluoroethylene (PTFE) was added to 20 g of distilled water as a dispersion medium, and stirred at a high speed of 2000 rpm using a high-speed mixer to form a binder solution.

9 g of YP50F (Kurary, Japan) commercially available as an electrode active material, and 0.05 g of super-P (super-P) as a conductive material were added to the binder solution, and then a paste-formed electrode composition was prepared using a high-speed mixer.

The composition for electrodes in a kneaded state was molded in a roll press molding machine until the surface became smooth to form a sheet of the composition for electrodes. The roll press molding machine is provided including an upper roll and a lower roll, and is formed by passing the electrode composition between the upper and lower rolls. The result of passing between the upper roll and the lower roll was folded in half, and the process of passing between the upper and lower rolls was repeated 15 times to obtain a sheet of the composition for electrodes having a smooth surface. Through rolling of the roll press forming machine, the electrode density can be improved and the thickness of the electrode can be controlled. The pressurization pressure applied to the electrode composition was about 10 ton/cm 2, and the heating temperature was about 60°C.

The electrode composition sheet formed using a roll press molding machine was punched into a size of 12 mm in diameter. The resulting product formed by punching was dried in a vacuum dryer. The drying was performed at a temperature of 150° C. for 24 hours.

The electrode sheet thus prepared was used as a supercapacitor electrode.

Using the prepared supercapacitor electrode as an anode and a cathode, a coin cell type supercapacitor having a diameter of 20 mm and a height of 3.2 mm was manufactured. At this time, in manufacturing the coin cell, an electrolyte containing 1M of TEABF ₄ in a propylene carbonate (PC) solvent was used, and TF4035 (manufactured by NKK, Japan) was used as the separator.

Table 1 below shows the moldability and mixing time of the electrode composition prepared according to Example 1 and the electrode composition prepared according to the comparative example. In addition, the electrode density of the supercapacitor electrode manufactured according to Example 1 and the electrode density of the supercapacitor electrode manufactured according to the comparative example were measured, and are shown in Table 1 below. In addition, the specific storage capacity of the supercapacitor manufactured according to Example 1 and the specific storage capacity of the supercapacitor manufactured according to the comparative example were measured and shown in Table 1 below.

Formability Mixing time
(minute) Electrode density (g/cc) Reserve capacity (F/cc) Comparative example usually 15 0.50 14.8 Example 1 Very good 10 0.65 16.5

6 shows the electrochemical analysis results of the supercapacitor manufactured according to Example 1 and the supercapacitor manufactured according to the comparative example.

Referring to Tables 1 and 6, the composition for an electrode prepared according to Example 1 was found to have excellent moldability compared to the composition for an electrode prepared according to the comparative example.

The supercapacitor electrode manufactured according to Example 1 was found to have a higher electrode density than the supercapacitor electrode manufactured according to the comparative example.

The supercapacitor manufactured according to Example 1 was found to have superior storage capacity compared to the supercapacitor manufactured according to the comparative example.

In the above, a preferred embodiment of the present invention has been described in detail, but the present invention is not limited to the above embodiment, and various modifications are possible by those of ordinary skill in the art.

110: cathode 120: anode
130: first lead wire 140: second lead wire
150: first separation membrane 160: second separation membrane
170: adhesive tape 175: winding element
180: sealing rubber 190: metal cap
192: gasket

Claims (10)

Electrode active material;
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 fluorine-containing binder based on 100 parts by weight of the electrode active material;
0.01 to 2 parts by weight of an additive based on 100 parts by weight of the electrode active material; And
It contains 100 to 300 parts by weight of a dispersion medium based on 100 parts by weight of the electrode active material,
The additive composition for a supercapacitor electrode, characterized in that it comprises 2-dimethylaminoethyl methacrylate (2-(dimethylamino)ethyl methacrylate).
The method of claim 1, wherein the composition for a supercapacitor electrode comprises 2-[(3-acrylamidopropyl dimethylammonio acetate) based on 100 parts by weight of the electrode active material (CBAA; 2-[(3-acrylamidopropyl) dimethylammonio] acetate) A composition for a supercapacitor electrode, characterized in that it further comprises 0.01 to 2 parts by weight.
The composition for a supercapacitor electrode according to claim 1, wherein the fluorine-containing binder comprises polytetrafluoroethylene (PTFE).
The method of claim 1, wherein the electrode active material has a specific surface area of 1500 ~ 3000 m ² / g of activated carbon having a specific surface area of 100 ~ 1000 m ² / g of graphene, carbon nanotubes (CNT; carbon nanotube) and the carbon nanofibers A composition for a supercapacitor electrode comprising at least one material selected from the group consisting of (carbon nanofiber).
Electrode active material, 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 fluorine-containing binder based on 100 parts by weight of the electrode active material, 0.01 to 2 parts by weight of an additive based on 100 parts by weight of the electrode active material And preparing a composition for a supercapacitor electrode by mixing 100 to 300 parts by weight of a dispersion medium based on 100 parts by weight of the electrode active material.
The composition for supercapacitor electrodes is pressed to form an electrode, or the composition for supercapacitor electrodes is coated on a metal foil or a current collector to form an electrode, or the composition for supercapacitor electrodes is pushed with a roller to form a sheet. Attaching to a metal foil or a current collector to form an electrode shape; And
Drying the resultant product formed in the form of an electrode to form a supercapacitor electrode,
The additive is a method of manufacturing a supercapacitor electrode, characterized in that it comprises 2-(dimethylamino)ethyl methacrylate.
The method of claim 5, wherein the composition for a supercapacitor electrode is 2-[(3-acrylamidopropyl dimethylammonio] acetate) based on 100 parts by weight of the electrode active material. Method of manufacturing a supercapacitor electrode, characterized in that it further comprises 0.01 to 2 parts by weight.
6. The method of claim 5, wherein the fluorine-containing binder comprises polytetrafluoroethylene (PTFE).
The method of claim 5, wherein the electrode active material has a specific surface area of 1500 ~ 3000 m ² / g of activated carbon having a specific surface area of 100 ~ 1000 m ² / g of graphene, carbon nanotubes (CNT; carbon nanotube) and the carbon nanofibers A method of manufacturing a supercapacitor electrode, comprising at least one material selected from the group consisting of (carbon nanofiber).
An anode made of a supercapacitor electrode manufactured by the method of claim 5;
A negative electrode made of a supercapacitor electrode manufactured by the method of claim 5;
A separator disposed between the anode and the cathode to prevent a short circuit between the anode and the cathode;
A metal cap in which the anode, the separator, and the cathode are disposed and an electrolyte is injected; And
Supercapacitor comprising a gasket for sealing the metal cap.
A first separator for preventing a short circuit, an anode made of a supercapacitor electrode manufactured by the method described in claim 5, a second separator for preventing a short circuit between the anode and the cathode, and manufactured by the method described in claim 5 A winding element in which a cathode made of a supercapacitor electrode is sequentially stacked to form a coiled roll;
A first lead wire connected to the negative electrode;
A second lead wire connected to the positive electrode;
A metal cap accommodating the winding element; And
It includes a sealing rubber for sealing the metal cap,
The winding element is a supercapacitor, characterized in that impregnated with an electrolytic solution in which a lithium salt is dissolved.

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