KR100672599B1 - Energy storage capacitor and method for fabricating the same - Google Patents

Abstract

The present invention provides an energy storage capacitor that can overcome the shortcomings in the current energy storage capacitor and improve its function by newly designing an electrode material that can be used for the anode and the cathode of the energy storage capacitor. In order to achieve the above, there are two electrode plates having at least one mixed electrode formed by mixing activated carbon and carbon fullerene having at least one of a positive electrode and a negative electrode, an electrolyte formed between the two electrode plates to flow a current; Located in the middle of the electrolyte is configured to include a separator for separating the electrolyte.

Super Capacitor, Mixed Electrode Material, Activated Carbon, Carbon Fullerene

Description

Energy storage capacitor and method for fabricating the same

1 is a view showing the ultra-high capacity expression principle of a general super capacitor

Figure 2a, 2b is a view showing the configuration of an energy storage capacitor according to the present invention

Figure 3a, 3b is a schematic diagram of the configuration of the energy storage capacitor electrode material according to the present invention

4 is a flowchart illustrating a process of manufacturing an electrode material according to an energy storage capacitor according to the present invention.

* Explanation of symbols for main parts of the drawings

10 porous porous nanocarbon electrode 20 electrolyte anion

30: electrolyte cation 100: electrode plate

110: activated carbon 120: carbon fullerene

121: pore 200: electrolyte

300: separator 400: metal film

500: energy storage capacitor 600: load

700: power

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to energy storage capacitors, and more particularly, to the construction and manufacturing method of energy storage capacitors using electrode materials suitable for realizing high output and energy density.

As an energy storage device for systems that require independent power supply such as various portable electronic devices and electric vehicles, or systems that regulate / supply instantaneous overloads, batteries are often considered first, but are not yet available for practical use. No suitable storage system has been developed.

In terms of energy input and output (ie, power) in the process of storing and utilizing electrical energy, capacitors perform better than batteries.

This is because the energy storage mechanism of the capacitor is due to the kinetic mechanism of very fast and reversible ions, unlike batteries which rely on thermodynamic mechanisms with redox processes, resulting in fast charging and charging and discharging efficiency. This is because it is higher than this battery and the charge / discharge repeated service life becomes very long.

The dual energy storage capacitor is a capacitor that functions as a conventional capacitor and has a mechanism for storing energy. It is an energy storage device that can serve as a bridge between a battery and a capacitor.

In terms of energy density and power density, an energy storage capacitor having intermediate characteristics between an electrolytic capacitor and a secondary battery has a shorter charging time, a longer life, and a higher output than a secondary battery, and is 10 times more energy than a conventional electrolytic capacitor. It is a dense system. That is, it means a system combining only the advantages of the power characteristics of the electrolytic capacitor and the high energy storage characteristics of the secondary battery.

The reason why the energy storage capacitor can act as a middle part between the battery and the existing capacitor, that is, the reason why it can have a high energy density and power density at the same time can be understood as follows.

An energy storage capacitor is a type of electrical energy storage device that converts and stores a chemical reaction into electrical energy by using an electrostatic orientation (electrochemical double-layer) of ions at an electrode / electrolyte interface.

That is, the capacitance (C) value in the existing capacitor is proportional to the contact area and inversely proportional to the distance between the positive and negative charges, that is, the thickness of the dielectric layer.

In the energy storage capacitor, the area of the energy storage capacitor is increased by using a nanoscale porous carbon electrode material. In addition, the energy storage capacitor is shown in FIG. As can be seen, the thickness of the dielectric layer is reduced to an ionic layer of 10 占 so that the value of capacitance can be increased to an ultra high capacity.

Such an energy storage capacitor has been described in other words as a super capacitor.

The supercapacitors are classified into two types according to their operation principle, one of which is an electrochemical double-layer capacitor which stores charge in an electric double layer of an electrode / electrolyte interface, and the other is a virtual capacitor. It is called a pseudo capacitor and is a redox capacitor that carries a change in the valence of transition metal ions on the surface of the transition metal oxide and stores charge or electrons.

Although the electric double layer capacitor has a theoretically large specific surface area using activated carbon, the area that can be calculated and used as the actual capacitance value is only 20-30% of the total.

This is because the size and the degree of adsorption of ions in the electrolyte to adhere to the activated carbon.

That is, the porous activated carbon may be classified into three types such as pore size of micro (20Å <), meso (20Å <pore size <100Å), and micropore (<100Å). . Of these, when the pore size is micropores, the ions in the electrolyte may not be a suitable size to enter the pores. Therefore, when the pore size of the activated carbon has a large number of micropores, it results in a dramatically increased specific surface area, which is an advantage of using activated carbon.

Therefore, maintaining a pore structure suitable for the size of a predetermined electrolyte ion is a way to increase the power density of the energy storage capacitor. However, this leads to costly and time-consuming loss of several heat treatments and additional processes.

In addition, the use of a single type of transition metal oxide in the redox capacitor is greatly reduced in cost and efficiency. For example, RuO ₂ has proved to be the most energy-saving property at present, but the disadvantage is that it is unsuitable for mass production due to its high price, and the charge-discharge curve is nonlinear in terms of efficiency.

Therefore, the present invention has been made to solve the above problems, overcoming the disadvantages in the current energy storage capacitor by newly designing the configuration of the electrode material that can be used for the anode and cathode of the energy storage capacitor and The purpose is to provide an energy storage capacitor that can improve its function.

Another object of the present invention is to provide an energy storage capacitor that effectively works in insertion and desorption of electrolyte ions by using a mixture of activated carbon and carbon fullerene (C60).

Still another object of the present invention is to provide an energy storage capacitor that uses a modified structure of activated carbon and carbon fullerene to facilitate the movement of electrons and contribute to the improvement of output and energy storage density.

Features of the energy storage capacitor according to the present invention for achieving the above object is two electrode plates having at least one mixed electrode formed of a mixture of activated carbon and carbon fullerene having any one of a positive electrode and a negative electrode, and An electrolyte is formed between the two electrode plates to flow a current, and a separator is disposed in the middle of the electrolyte to separate the electrolyte.

Preferably, the electrode plate composed of the mixed electrode is characterized in that it further comprises a metal film on top.

Preferably, the metal film has a thickness of several tens of micrometers (micrometer).

Preferably, the metal film is made of Al or Cu.

이상 3000

이하를 갖는 활성탄소와, 기공크기가 10 nm이하인 탄소플러렌으로 구성되는 것을 특징으로 한다.Preferably the hybrid electrode has a specific surface area of 1500

More than 3000

It is characterized by consisting of activated carbon having the following and a carbon fullerene having a pore size of 10 nm or less.

Preferably the mixed electrode is characterized in that consisting of a thickness of less than 200㎛.

Preferably the mixed electrode is characterized in that the ratio of the activated carbon to 50% or more of the total ratio.

Preferably the carbon fullerene is characterized in that it is composed of any one of an insulating carbon fullerene and a conductive carbon polymer.

Preferably, the insulating carbon fullerene is characterized by consisting of C60 having a bucky ball structure consisting of 60 carbons.

Preferably, the conductive carbon polymer is characterized in that it is composed of any one of C 60 (OH) n, C 60 (H) n and Na x (C 60) formed by breaking the cage structure of the fullerene.

Preferably the electrolyte is characterized by consisting of any one of an aqueous electrolyte and an organic electrolyte.

Preferably, the separator is characterized in that it is composed of any one of polypropylene and polyethylene series.

Features of the manufacturing method of the energy storage capacitor according to the present invention for achieving the above object is the step of preparing an electrode material in the form of a slurry (slurry) by mixing activated carbon and carbon fullerene, the top and bottom of the current collector Coating an electrode material manufactured in the form of the slurry on at least one of the above, applying a predetermined pressure to the coated current collector with a roller or a phrase to form an electrode material having a predetermined thickness, and the coated electrode material Performing vacuum drying and heat treatment, and pressing the separator in a sandwich form with a separator between the formed electrode materials, and injecting an electrolyte.

Preferably the coating step is characterized in that the coating further comprises a metal film after the electrode material coating.

Preferably, when the electrolyte is an aqueous electrolyte, the solvent of the aqueous electrolyte is characterized in that at least one of distilled water (Distilled water), 2-butoxy ethanol and iso-propyl alcohol.

Preferably, when the electrolyte is an organic electrolyte, the solvent of the organic electrolyte quality is NMP (N-methyl pyrrolidinone) is characterized in that.

부터 3000

을 갖고, 상기 탄소플러렌의 혼합 함량이 5wt% 부터 50 wt%인 것을 특징으로 하는 에너지 저장형 커패시터 제조방법.Preferably the specific surface area of the activated carbon is 1500

From 3000

It has an energy storage capacitor manufacturing method, characterized in that the mixed content of the carbon fullerene is from 5wt% to 50wt%.

Preferably, the step of preparing the electrode material is characterized in that to produce a slurry (slurry) by mixing a binder and a plasticizer in a predetermined ratio.

Preferably, when the electrolyte is an aqueous electrolyte, the binder is characterized in that the SBR (Stylene Butadien Rubber).

Preferably, when the electrolyte is an organic electrolyte, the binder is characterized by using at least one of polyvinylidene fluoride (PVDF) and polyacrylic vinyl copolymer (PACo).

Preferably the plasticizer is characterized in that the polyethylene glycol (PEG).

Preferably the binder is characterized in that the mixing ratio is less than 10 wt%.

Preferably, the predetermined thickness of the electrode material is characterized in that it has within 200㎛.

Preferably the coating of the current collector is characterized in that the coating using a spray (spray) or doctor blade (doctor blade) method.

Preferably the heat treatment is characterized in that performed between 100 to 500 degrees.

Preferably, the carbon fullerene is formed of any one of an insulating carbon fullerene and a conductive carbon polymer.

Preferably, the insulating carbon fullerene is formed of C60 having a bucky ball structure made of 60 carbons.

Preferably, the conductive carbon polymer is formed of any one of C 60 (OH) n, C 60 (H) n and Na x (C 60) formed by breaking the cage structure of the fullerene.

Other objects, features and advantages of the present invention will become apparent from the following detailed description of embodiments with reference to the accompanying drawings.

In the present invention, the carbon fullerene described above may be divided into two types. The full spherical carbon fullerene has the property of an insulator, and the carbon fullerene has the property of conduction because the cage structure is broken and the activator is attached. At this time, in order to have conductivity, all carbon polymers regardless of the number of carbon bonds should be used. Therefore, the carbon fullerenes mentioned in the present invention are referred to as insulating carbon fullerene and conductive carbon polymer, respectively.

An embodiment of an energy storage capacitor and a method of manufacturing the same according to the present invention will be described with reference to the accompanying drawings.

Figure 2a is a view showing the configuration of the energy storage capacitor according to the present invention, Figure 2b is a view showing a circuit diagram of the energy storage capacitor according to the present invention.

As shown in FIG. 2A, the structure of the energy storage capacitor includes two electrode plates 100 having at least one mixed electrode formed of a mixture of activated carbon and carbon fullerene having at least one of a positive electrode and a negative electrode, and the two electrodes. It is composed of an electrolyte 200 formed between the plate 100 to flow a current, and a separator 300 is located in the middle of the electrolyte 200 to separate the electrolyte.

In this case, the electrode plate 100 composed of the mixed electrode further includes a metal film 400 thereon.

In addition, as shown in FIG. 2B, the energy storage capacitor 500 is implemented to be connected to the power source 700 and the load 600 in parallel.

A schematic diagram of the mixed electrode 100 is shown in detail in FIGS. 3A and 3B.

As shown in FIGS. 3A and 3B, the structure of the electrode material in which insulating carbon fullerene and conductive carbon fullerene are mixed to reduce internal resistance and at the same time efficiently use specific surface area for the construction of the electrode material of the energy storage capacitor.

That is, FIG. 3A is a schematic view of the mixture of activated carbon and carbon fullerene, which is a kind of carbon, to allow the fullerene to act effectively in insertion and desorption of electrolyte ions. At this time, the carbon fullerene is preferably composed of a Bucky ball structure consisting of C60, 60 carbon.

In addition, Figure 3b is a kind of activated carbon and fullerene mixed with C60 (OH) n or C60 (H) n or Nax (C60) (hereinafter referred to as conductive carbon polymer) formed by breaking the cage structure of the fullerene It is a schematic diagram which contributes to the improvement of an output and an energy storage density by making electron movement smooth. In this case, the modified carbon fullerene refers to all carbon polymers made of carbon (element symbol C) regardless of the number of bonds.

이상 3000

이하를 갖도록 구성되며, 상기 탄소플러렌 및 전도성 탄소중합체는 기공크기가 10 nm이하이고 혼합함량이 전체함량에 1 wt%부터 50 wt%까지를 갖도록 구성된다.In this case, the activated carbon has a specific surface area of 1500

More than 3000

The carbon fullerene and the conductive carbon polymer have a pore size of 10 nm or less and a mixing content of 1 wt% to 50 wt% in the total content.

In addition, the electrolyte may be an aqueous electrolyte or an organic electrolyte, and the separator is preferably polypropylene or polyethylene series.

When described in detail with reference to the accompanying drawings, a method for manufacturing an energy storage capacitor according to the present invention configured as described above.

4 is a flowchart illustrating a process of manufacturing an electrode material according to the energy storage capacitor according to the present invention.

Referring to FIG. 4, first, the mixing ratio is 50 wt% or more of the activated carbon, and the activated carbon is mixed with the insulating carbon fullerene or the conductive carbon fullerene (S10).

At this time, the insulating carbon fullerene is preferably composed of a Bucky ball structure consisting of C60, 60 carbon.

In addition, the conductive carbon fullerene is a kind of fullerene that is composed of a C 60 (OH) n or C 60 (H) n or Na x (C 60) structure (hereinafter referred to as a conductive carbon polymer) formed by breaking the cage structure of the fullerene. desirable. In this case, the modified carbon fullerene (carbon polymer) refers to all carbon polymers made of carbon (element symbol C) regardless of the number of bonds.

Examples according to the mixed conditions of the activated carbon and carbon fullerene are as follows.

Example 1

When using an aqueous electrolyte,

부터 3000

을 갖는 활성탄소와 혼합 함량이 1wt% 부터 50 wt%까지인 탄소플러렌에 적절한 바인더와 가소제를 적당한 비율로 혼합하여 슬러리(slurry) 형태로 제조한다.1500 specific surface area

From 3000

An activated carbon having a mixed content of 1 wt% to 50 wt% of carbon fullerene and a suitable binder and a plasticizer are mixed in an appropriate ratio to prepare a slurry.

At this time, when using a solvent as a water system, distilled water (Distilled water) and 2-butoxy ethanol and iso-propyl alcohol is used. In addition, SBR (Stylene Butadien Rubber) is used as the binder, and the content is mixed below 10 wt%. In addition, polyethylene glycol (PEG) is used as the plasticizer.

Example 2

When using an organic electrolyte,

부터 3000

을 갖는 활성탄소와, 혼합 함량이 1wt% 부터 50 wt%까지인 탄소플러렌에 적절한 바인더와 가소제를 적당한 비율로 혼합하여 슬러리(slurry) 형태로 제조한다.1500 specific surface area

From 3000

It is prepared in the form of a slurry by mixing an activated carbon having an appropriate ratio and a suitable binder and a plasticizer in a carbon fullerene having a mixed content of 1wt% to 50wt%.

In this case, NMP (N-methyl pyrrolidinone) is used as a solvent that can be used when the solvent is used as an organic system. And as the binder, PVdF (poly vinylidene fluoride) or PACo (polyacrylic vinyl copolymer) is used, the content is mixed below 10 wt%. In addition, polyethylene glycol (PEG) is used as the plasticizer.

Subsequently, the mixed electrode manufactured in the slurry form is coated on the current collector (S20). The metal film 400 is made of Al or Cu having a thickness of several tens of micrometers (micrometer).

At this time, the coating on the current collector using a doctor blade (doctor blade) method which is a kind of spray (spray) or tape casting (Tape casting). And the solvent of the prepared slurry can be applied to both aqueous and non-aqueous.

Then, the coated current collector is applied with a predetermined pressure with a roller or a place to form an electrode material having a thickness of 200 μm or less (S30).

Thereafter, the coated electrode material is subjected to vacuum drying and heat treatment (S40).

That is, moisture and organic solvents are removed in a vacuum drying furnace and heat treatment is performed within 200 degrees in a box furnace. By doing so, it is possible to improve the surface quality of the coating electrode by evaporating all the remaining organic solvent or water and maximizing the role of the binder.

At this time, pressure is applied to match the thickness of the coating layer and heat treatment is performed between 100 and 500 degrees to achieve densification of the coating layer.

Finally, after pressing in a sandwich form with a separator interposed therebetween, an electrolyte is injected to manufacture an energy storage capacitor (S40). At this time, the solvent of the injected electrolyte can be applied to both aqueous and non-aqueous.

Those skilled in the art will appreciate that various changes and modifications can be made without departing from the spirit of the present invention.

Therefore, the technical scope of the present invention should not be limited to the contents described in the embodiments, but should be defined by the claims.

An energy storage capacitor and a method of manufacturing the same according to the present invention as described above have the following effects.

First, the present invention increases energy use efficiency and maximizes performance and function of the battery when used in combination with a secondary battery through the composition of an electrode material that can make the most of the advantages of the conventional energy storage capacitor through the present invention. You can expect an extension.

Second, the application of the present invention can maximize the use of energy storage capacitors through the modification of the electrode material design, which can be utilized in various elements of various power systems using electric energy, thereby having enormous demand potential. Can be. At its closest, the focus is on its use as an energy source to be replaced with secondary batteries.

Third, by applying the present invention, it is expected that the present invention can be applied as an inexpensive and excellent battery replacement capacitor to all portable small electronic devices.

Claims (33)

Two electrode plates having at least one mixed electrode formed by mixing the activated carbon and carbon fullerene such that the activated carbon is 50 wt% or more, An electrolyte formed between the two electrode plates to flow a current; Energy storage capacitor, characterized in that it comprises a separator located in the middle of the electrolyte to separate the electrolyte. The method of claim 1, The electrode plate composed of the mixed electrode further comprises a metal film on top of the energy storage capacitor. The method of claim 2, The metal film is energy storage capacitor, characterized in that having a thickness of several tens (micrometer). The method of claim 2, The metal film is an energy storage capacitor, characterized in that consisting of Al or Cu. The method of claim 1, The mixed electrode has a specific surface area of 1500

More than 3000

Energy storage capacitor, characterized in that consisting of activated carbon having a pore size and carbon fullerene having a pore size of 10 nm or less. The method of claim 1, The energy storage capacitor, characterized in that the mixed electrode is composed of a thickness of less than 200㎛. delete. The method of claim 1, The carbon fullerene is an energy storage capacitor, characterized in that composed of any one of an insulating carbon fullerene and a conductive carbon polymer. The method of claim 8, The insulating carbon fullerene is an energy storage capacitor, characterized in that consisting of C60 having a bucky ball structure consisting of 60 carbon. The method of claim 8, The conductive carbon polymer is an energy storage capacitor, characterized in that consisting of any one of C 60 (OH) n, C 60 (H) n and Na x (C 60) formed by breaking the cage structure of the fullerene. The method of claim 1, The electrolyte is an energy storage capacitor, characterized in that consisting of any one of an aqueous electrolyte and an organic electrolyte. The method of claim 1, The separator is an energy storage capacitor, characterized in that composed of any one of polypropylene and polyethylene series. Making an activated carbon of 50wt% or more, preparing an electrode material mixed with the activated carbon and carbon fullerene in a slurry form; Coating an electrode material manufactured in the form of the slurry on at least one of upper and lower portions of a current collector; Applying a predetermined pressure to the coated current collector to form an electrode material having a predetermined thickness; Performing vacuum drying and heat treatment on the coated electrode material; An energy storage capacitor manufacturing method comprising the step of injecting an electrolyte after pressing the separation membrane between the formed electrode material. The method of claim 13, The coating step is a method of manufacturing an energy storage capacitor, characterized in that the coating further comprises a metal film after the electrode material coating. The method of claim 14, The metal film is energy storage capacitor manufacturing method characterized in that the coating to a thickness of several tens (micrometer). The method of claim 14, The metal film is an energy storage capacitor manufacturing method, characterized in that formed of Al or Cu. The method of claim 14, The electrode material is energy storage capacitor manufacturing method characterized in that the mixing ratio is formed so that the active carbon is more than 50wt% of the total ratio. The method of claim 13, The electrolyte is a method of manufacturing an energy storage capacitor, characterized in that at least one of an aqueous and non-aqueous electrolyte. 19. The method of claim 18, wherein when the electrolyte is an aqueous electrolyte, The solvent of the aqueous electrolyte is an energy storage capacitor, characterized in that at least one of distilled water (Distilled water), 2-butoxy ethanol and iso-propyl alcohol. The method of claim 18, wherein when the electrolyte is an organic electrolyte, Energy storage capacitor, characterized in that the solvent of the organic electrolyte is NMP (N-methyl pyrrolidinone). The method of claim 18, The specific surface area of the activated carbon is 1500

From 3000

Energy storage capacitor manufacturing method characterized in that it has a. delete. The method of claim 13, The manufacturing of the electrode material is a method of manufacturing an energy storage capacitor, characterized in that to produce a slurry (slurry) by mixing a binder and a plasticizer in a predetermined ratio. The method of claim 23, wherein when the electrolyte is an aqueous electrolyte, The binder is an energy storage capacitor, characterized in that the SBR (Stylene Butadien Rubber). The method of claim 23, wherein when the electrolyte is an organic electrolyte, The binder is an energy storage capacitor, characterized in that using at least one of PVdF (poly vinylidene fluoride) and PACo (polyacrylic vinyl copolymer). The method of claim 23, The plasticizer is an energy storage capacitor, characterized in that the polyethylene glycol (PEG). The method of claim 23, The binder is an energy storage capacitor, characterized in that the mixing ratio is less than 10 wt%. The method of claim 13, The predetermined thickness of the electrode material has a method of producing an energy storage capacitor, characterized in that less than 200㎛. The method of claim 13, The coating of the current collector is an energy storage capacitor manufacturing method characterized in that the coating using a spray (spray) or doctor blade (doctor blade) method. The method of claim 13, The heat treatment is an energy storage capacitor manufacturing method, characterized in that performed between 100 to 500 degrees. The method of claim 13, The carbon fullerene is energy storage capacitor manufacturing method characterized in that formed of any one of an insulating carbon fullerene and a conductive carbon polymer. The method of claim 31, wherein The insulating carbon fullerene is energy storage capacitor manufacturing method, characterized in that formed of C60 having a buckle (bally ball) structure consisting of 60 carbon. The method of claim 31, wherein The conductive carbon polymer is an energy storage capacitor manufacturing method, characterized in that formed of any one of C 60 (OH) n, C 60 (H) n and Na x (C 60) formed by breaking the cage structure of the fullerene.

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