KR20190110944A - Vacuum Hybrid Supercapacitor - Google Patents

Abstract

The present invention relates to a vacuum hybrid supercapacitor which makes electric charges charged in a vacuum and has dual charging properties, and more particularly, to a vacuum hybrid supercapacitor having electrodes and an electrolyte, which has the electrodes installed inside a vacuum chamber and fills the vacuum chamber with the electrolyte comprising ion-containing fullerenes or ion-containing fullerene salts, thereby performing charging by means of the ions contained in the fullerenes and performing charging by means of the fullerenes. The present invention enables primary charging using the ions contained in the ion-containing fullerenes and secondary charging using the degenerated molecular trajectory of the ion-containing fullerenes. Compared with performing only charging by means of the ions contained in the ion-containing fullerenes, the charging capacity is significantly increased six times, and the charging is further facilitated by the ions contained in the fullerenes. Further, the charging is performed in the vacuum to fundamentally block a problem such as decomposition of the electrolyte, thereby enabling the charging even with a voltage of hundreds of thousands of kv. Further, by using the fullerenes of a nanosize as the electrolyte, the energy storage density can be significantly increased, thereby making it possible to produce a compact and lightweight vacuum hybrid supercapacitor and increasing the charging and discharging characteristics.

Description

Vacuum Hybrid Supercapacitor

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vacuum hybrid supercapacitor in which charge charging action is carried out in a vacuum and also double charging characteristics. In particular, an electrode is installed inside a vacuum chamber, and This embedded fullerene (hereinafter referred to as "ion-containing fullerene") is used as an electrolyte, and an electrode is composed of a material having polarization and conductivity with respect to the ion-containing fullerene, and then the voltage above the reduction potential of the ion-containing fullerene. It is a vacuum hybrid supercapacitor of a completely new concept that the charging is performed at, so that charging (primary charging) by ions contained in the ion-containing fullerene and charging by the ion-containing fullerene itself (secondary charging) are performed.

The present invention is capable of charging from a very low voltage to a voltage of up to several hundred thousand kV, as well as dramatically improving the charging capacity, improving the charging and discharging characteristics, and has the advantages of being physically and chemically stable. In addition, the use of fullerene, a nano-sized molecule, has the advantage of increasing energy density, miniaturization, and weight reduction.

In the present specification, a new concept of a supercapacitor in which both the charge by the ions contained in the ion-containing fullerene and the charge by the ion-containing fullerene itself are performed is referred to as a "hybrid capacitor". Same as below.

In addition, in this specification, an electrode which has polarization with respect to an ion-containing fullerene means the electrode which forms a polarization like an activated carbon electrode, but does not physically couple an ion-containing fullerene and an electrode. Same as below.

In addition, in the present specification, the electrode having polarity and conductivity with respect to the ion-containing fullerene is, like activated carbon doped with a halogen element to have conductivity, the ion-containing fullerene does not have to be physically bonded to the electrode. It refers to an electrode capable of electron transfer to the ion-encapsulated fullerene through. In other words, the ion and the electrode contained in the ionic fullerene form a polarization, but the ion-full fullerene itself refers to an electrode capable of moving electrons through the electrode. Same as below.

As is well known, there are two ways to store electrical energy. The first is an electrolytic storage method that stores electrical energy as chemical energy by using redox reactions of ions. The second is an electrostatic storage method that stores electrical energy as electrical energy itself by using polarization between two electrodes. Electrostatic storage method.

Secondary batteries such as lead acid batteries, nickel cadmium batteries, nickel hydrogen batteries, and lithium ion polymer batteries are the first electrolytic storage that can be repeatedly reused for charging and discharging through reversible interconversion between chemical and electrical energy. An example of the method is a second electrostatic storage method, which is a capacitor that allows repetitive charge and discharge using polarization between two pole plates. In the present specification, the battery by the electrolytic storage method is referred to as a "chemical battery". Same as below.

Chemical batteries have the advantage of being able to store large amounts of energy due to their high energy density, while converting between electrical and chemical energy causes loss of energy conversion, generates heat, risks of fire and explosion, Since the energy cannot be charged and discharged in a short time, the charging time is long, the charging is difficult, the discharge characteristics are deteriorated, the life is short, and the pollutants are discharged.

Capacitors have the advantages of no energy conversion loss during charging and discharging, no heat generation, no risk of explosion, long life to an unlimited number, fast charging and rapid discharge, no pollution emissions, The low energy density has the disadvantage of not storing large amounts of energy.

Therefore, research on energy storage devices having both the advantages of chemical batteries and the advantages of capacitors, but without the disadvantages, has been continuously conducted.

As technology has advanced, supercapacitors have been developed that significantly increase the energy density of capacitors to enable high-capacity charging, enabling energy storage to meet the advantages of chemical batteries and capacitors.

Unlike electrolytic batteries that use chemical reactions, supercapacitors are electrochemical mechanisms whereby voltages across the unit cell electrodes move along the electric field, and the transferred ions are adsorbed on the electrode surface to accumulate charge. It is also referred to as an electrochemical capacitor (Electrochemacal capacitor) separately from the electrolytic or electrostatic. Since the supercapacitor utilizes ion migration to the electrode and electrolyte interface and charging by surface chemical reaction, rapid charge and discharge is possible, high charge and discharge efficiency and semi-permanent cycle life are possible, and higher power than chemical battery. It is possible and environmentally friendly, making it the next generation energy storage device for electric vehicles, mobile phones, camera flashes, and drones.

Such supercapacitors are classified into Electric Double Layer Capacitors (ELDC), Pseudo Capacitors, and Hybrid Capacitors according to electrodes and mechanisms used.

In general, an electric double layer capacitor includes two porous electrodes facing each other, an electrolyte filled between the porous electrodes, a separator for electrically separating the porous electrodes, and an electrode formed thereon. The basic structure is made of a current collector and a case. In the electric double layer capacitor, when a potential difference is applied across the electrodes, positive and negative charges are collected at each of the two electrodes, and thus, opposite charge ions are collected around each electrode in the electrolyte to form an electrical double layer. The storage occurs by using the phenomenon that the surface area is increased due to the porous electrode and the electric double layer is formed to enable a large amount of energy storage.

A pseudocapacitor is a capacitor that uses a redox reaction of an electrode and an electrochemical oxide reactant. An electric double layer capacitor can store charge close to the surface of an electrode material as compared to a double layer formed on an electrode surface, so that a high energy density can be obtained. One capacitor.

Hybrid capacitors use asymmetric electrodes with different operating voltage ranges and specific capacitances for the positive and negative electrodes, so that one electrode uses high-capacity electrode materials and the other uses high-output electrode materials to improve capacitance characteristics. It is a capacitor which minimizes a high output characteristic loss and has high operating voltage and high energy density.

In order to further increase the capacity and size of supercapacitors, and to improve charge and discharge characteristics, more research is being conducted. This research has been focused on the study of electrode materials and electrolytes having a large surface area and high conductivity and electrochemical stability.

Among the electrode materials to increase the specific surface area of the electrode, carbon electrode materials that attract a lot of attention include activated carbon, active carbon fiber, amorphous carbon, and carbon aerogel. In order to further increase the specific surface area of these electrodes, various methods of processing have been performed. Activated carbon has a pore of 2 to 50 nm and a surface area of 1,000 to 3,000 m 2 / g, and has high electrical conductivity and is easily used for molding.

The electrolyte is classified into water-soluble and non-water-soluble (organic). In the case of the water-soluble electrolyte, the output characteristics are high while the energy density is low. In the case of the organic electrolyte, the resistance characteristics are low while the energy density is high. The characteristics of the electrolyte vary depending on the solvent and the solute, and many studies have been conducted in consideration of the internal resistance, the solubility, and the chemical reaction rate of the solvent.

As technology advances, graphene and carbon nanotubes can be used as electrodes, resulting in higher capacity and improved characteristics of supercapacitors.

Graphene is a material in which two carbons are connected to each other in a hexagonal shape to form a honeycomb two-dimensional planar structure. Carbon nanotubes are formed by connecting six hexagonal shapes consisting of six carbons to each other to form a tubular shape. The diameter can be different. Republic of Korea Patent Application No. 10-2015-7006745 "Highly dispersible graphene composition, its manufacturing method and electrode of a lithium ion secondary battery containing a highly dispersible graphene composition", Republic of Korea Patent No. 10-1486658 "High Performance Super Graphene-based electrode materials for capacitor electrodes and supercapacitors including the same are described as an example of a technique using graphene as an electrode, and Korean Patent Application No. 10-2013-7033691 "Carbon Nanotube-Based Electrode and Rechargeable battery ", Republic of Korea Patent No. 10-1600185" Battery electrode and its manufacturing method "describes an example of a technique using a carbon nanotube as an electrode.

As nanotechnology advances and studies on carbon materials intensify, fullerenes, which are other forms of carbon, have been discovered and applied to supercapacitors.

Fullerene is a pentagon of five carbons and a hexagon of six carbons combined in a spherical spherical shape to form a hollow, and there are various forms of fullerenes depending on the number of carbons used. There are fullerenes such as C60, C70, C72, C78, C82, C90, C94, C96 and the like, and some have larger carbon numbers. Such fullerenes have the shape of a soccer ball or a sphere, similar to a soccer ball, and have structural characteristics in the hollow phase.

Fullerene has excellent physical and chemical properties due to the carbon ring arrangement and the unique structure of the hollow phase. Specifically, it has many useful physical and chemical properties, such as strong antioxidant properties, adsorption properties, catalytic properties (decomposability of adsorbed materials), electromagnetic wave absorption properties, electrical conductivity and higher strength than diamond.

Fullerene is made of carbon black or graphite as an raw material, either artificially by the arc discharge method or continuous combustion method, or extracted from natural minerals. Korean Patent No. 10-1515534 "Method for producing fullerene for electrode material" is a fullerene is prepared from a natural mineral such as silicate containing a fullerene or similar fullerene using an electrochemical method or a polar solvent extraction method. Here's how.

Recently, studies on increasing the capacity and improving the characteristics of supercapacitors by using the characteristics of fullerenes in supercapacitors have been continued. Republic of Korea Patent No. 10-0773585 "Method of manufacturing a fuel cell electrode" is a fuel cell using a fullerene, and Republic of Korea Patent No. 10-1251635 "Fullerene-based secondary battery electrodes" is a fullerene material n≥100 Electrode technology for batteries having a carbon component of Cn is presented.

However, the above-described conventional techniques use activated carbon, graphene, carbon nanotubes, or fullerene as electrode materials to increase the surface area of the electrode, and have improved the capacity and characteristics of the supercapacitor by using the surface area of the expanded electrode. There was a limitation that it was limited to this electrode. In addition, the use of polarization and surface chemical reactions is not satisfactory for the study of electrolytes, and there are problems such as limitations in improving energy storage capacity and energy storage density.

In addition, the conventional technologies have a problem in that the electrolyte loses its function when the charging voltage is increased and charging over a predetermined voltage is impossible, and therefore, the charging of the high voltage is practically impossible.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems. In particular, after the electrode is installed inside the vacuum chamber and the supercapacitor is formed using the ion-containing fullerene as the electrolyte, the reduction potential of the ion-containing fullerene is higher than The charging is performed by the voltage to charge by the ions contained in the ion-full fullerene, and the charge by the ion-full fullerene itself to significantly improve the energy storage capacity and energy storage density, as well as physical and chemical extremely It is to provide a stable hybrid supercapacitor.

That is, there is no decomposition of the electrolyte by removing the electrolyte by using the ion-containing fullerene as the electrolyte in the vacuum chamber, thereby eliminating the electrolyte, thereby enabling charging at a high voltage of several hundred thousand kV.

In addition, by forming an electrode with a material having polarity and conductivity to the ion-containing fullerene to fill the electrolyte containing the ion-containing fullerene between the electrodes, by applying a voltage higher than the reduction potential of the ion-containing fullerene to charge, Firstly, the primary charging is performed by the ions contained in the iontofullerene, and secondly, the secondary charging is performed by the degenerate molecular orbital of the iontofullerene, thereby dramatically reducing the energy storage capacity and the energy storage density. It is an improvement.

The present invention "vacuum hybrid supercapacitor" is a supercapacitor having an electrode and an electrolyte, the electrode is installed inside the vacuum chamber, and the fullerene is filled with an electrolyte containing a fullerene or a salt thereof containing ions in the vacuum chamber. It is characterized by the technical configuration that primary charging is performed by the ions contained in the secondary charge and secondary charging is performed by the fullerene itself.

In addition, any one of the electrodes is configured to have polarity and conductivity with respect to the fullerene containing ions, and the other is configured to have polarity with respect to the fullerene containing ions, or is configured to have both polarization and conductivity do.

In particular, the present invention "vacuum hybrid supercapacitor" includes an electrode inside a vacuum chamber, an ion-full fullerene as an electrolyte, and an electrode formed of a material having polarity and conductivity with respect to the ion-full fullerene, and then the ion-containing. By charging at a voltage higher than the reduction potential of fullerene, the primary charging by the ions contained in the ion-containing fullerenes and the secondary charging by the degenerate molecular trajectory of the ion-containing fullerenes are performed.

In addition, since the charge is made in a vacuum atmosphere, thereby preventing the problem such as decomposition of the electrolyte at the source, there is an effect that can be charged at a voltage of several hundred thousand kV.

In addition, compared to the case of only charging by the ions contained in the ion-containing fullerenes, there is an effect that the charge capacity is increased by 6 times, and the charging is more easy due to the ions contained in the fullerenes.

In addition, by using fullerene, which is a nano-sized molecule, as an electrolyte, the energy storage density is significantly increased, thereby making it possible to manufacture small and light weights, and to improve charging and discharging characteristics.

In addition, the use of physically and chemically very stable fullerenes has the effect of enabling a very stable physical and chemical energy storage.

1A is a schematic diagram showing a discharge state of a hybrid supercapacitor of the present invention;
Figure 1b is a schematic diagram showing the state of charge of the hybrid supercapacitor of the present invention,
Figure 1c is a schematic diagram showing an enlarged state of charge of the hybrid supercapacitor of the present invention,
Figure 1d is a block diagram showing the configuration of the present invention vacuum hybrid supercapacitor,
Figure 2a is a perspective view showing the structure of graphene,
2B is a perspective view showing a bonding direction for forming a graphene electrode having polarity;
Figure 2c is a perspective view showing the bonding direction for forming a conductive graphene electrode,
3 is a perspective view showing the chirality of carbon nanotubes,
Figure 4a is a structural diagram showing the bonding of fullerenes,
4B is a structural diagram showing bonding on the xy plane of fullerenes;
4A is a structural diagram showing another bond on the xy plane of fullerene,
5 is a schematic diagram showing adsorption of fullerene using the Miller surface 111 of gold,
6 is a graph showing the CV curve of Li @ C60 according to the present invention.
Figure 7a, b is one side view showing an example of a vacuum chamber applied to the present invention.

In the following description of the present invention by way of example, the same reference numerals refer to the same configuration, and additional descriptions that may overlap or limit the meaning of the invention may be omitted in describing the embodiments of the present invention. .

Prior to the detailed description, the concept of the invention, in spite of the singular form of the present disclosure, in light of the circumstances in which the singular / plural is not clearly distinguished in the use of Korean language and the general terminology used in the art. It is used in the sense that it includes plural expressions unless otherwise contradictory or clearly different from each other. In addition, 'includes', 'haves', 'comprises', 'comprises', and the like, as described or described herein, may indicate the presence or addition of one or more other features or components or combinations thereof. It should be understood that it is not excluded in advance.

In one aspect, the present invention relates to a vacuum chamber and an electrolyte filled in the vacuum chamber.

In another aspect, the present invention provides a vacuum in which a vacuum chamber, an ion-containing fullerene filled in the vacuum chamber, a current collector bonded to an inner surface of the vacuum chamber, and an electrode having both polarization or polarity and conductivity are selectively provided. It relates to a hybrid supercapacitor.

As shown in FIG. 1D, the vacuum hybrid supercapacitor according to the present invention includes electrodes 20 and 20 'respectively formed in current collectors 10 and 10' in the vacuum chamber 40, and It consists of an electrolyte 30 that is filled between the electrodes (20, 20 ').

The current collectors 10 and 10 'are made of a metal such as aluminum (Al) or copper (Cu), and both current collectors 10 and 10' facing each other are made of the same material or different materials. can do. For example, the first current collector 10 may be made of aluminum, and the second current collector 10 ′ may be made of copper.

Any one of the first electrode 20 formed on the first current collector 10 and the second electrode 20 'formed on the second current collector 10' has both polarization and conductivity with respect to the ion-containing fullerene. The other may be configured to have only polarity with respect to the ion-containing fullerene or may be configured to have both polarity and conductivity.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The vacuum hybrid supercapacitor of the present invention is based on a vacuum chamber, an electrode, a current collector, and an electrolyte.

Current collector (10)

The current collectors 10 and 10 'according to the present invention are configured to be bonded or deposited on the inner surface or the outer surface of the vacuum chamber, which will be described later.

For example, the present invention is easy to purchase in the order of potential consisting of Au-Pt-Ag-Cu-H2-Pb-Sn-Ni-Co-Cd-Fe-Cr-Zn-Al-Mg-Na-Ka, and is easy to process. This excellent copper and aluminum are used. Preferably, copper (Cu) is used as the positive electrode current collector, and aluminum (Al) is used as the negative electrode current collector, and the positive electrode current collector and the negative electrode current collector are joined to surfaces facing each other in the vacuum chamber, respectively.

Electrode 20

The electrode according to the present invention comprises a first electrode and a second electrode provided on the opposite side.

The first and second electrodes 20 and 20 ′ may be configured by bonding or growing to a current collector, and an electrode having both polarity or polarity and conductivity may be selectively configured.

The first and second electrodes are based on activated carbon, and any one of graphene, graphite, carbon nanotubes, fullerene, and teflon may be used.

The activated carbon may be made of sawdust activated carbon, yashigara activated carbon, pichcokes activated carbon, phenol resin activated carbon, polyacrylonitrile activated carbon, cellulose activated carbon, or the like. Ruthenium oxide, manganese oxide, cobalt oxide, and the like. Conductive polymer materials may also be used, and examples thereof include polyaniline membranes, polypyrrole membranes, polythiophene membranes, poly (3,4-ethylenedioxythiophene) membranes, and the like.

Preferably, activated carbon or Teflon is bonded to the current collector using a binder, or it is preferable to bond the graphene or fullerene so as to have polarity.

Porous activated carbon with polarity is made by carbonizing coconut fiber. The activated carbon thus produced is bonded to a current collector using a binder to form an electrode having polarity.

As another example, the electrode of the present invention may be composed of an electrode having both polarization and conductivity. For example, activated carbon having polarity and conductivity is made by doping an activated carbon having polarity with a halogen element such as iodine (I3).

When the activated carbon is bonded to the current collector using the binder, an electrode having polarization and conductivity is made.

Electrode according to the present invention is also composed of carbon nanotubes, graphene, fullerene, preferably made of polarity, but in some cases made of an electrode having both polarity and conductivity is bonded to the current collector by the bonding agent Can be.

Carbon nanotubes are already known, the hexagonal shape consisting of six carbons are connected to each other to form a tubular shape can vary the diameter of the tube according to the synthetic conditions.

As shown in the figure, the chirality can be controlled to control electrical properties, which can be used to make the carbon nanotubes have only polarity with respect to ion-containing fullerenes, or have both polarity and conductivity. Therefore, when growing carbon nanotubes on a current collector, the chirality is controlled so that there is no conductivity, and an electrode having only polarity with respect to the ion-pooferene is made. It is possible to make an electrode having both conductivity.

The chirality of carbon nanotubes is a chiral vector index according to the hexagonal structure formed, and includes a chair shape (n = m), a spiral shape (n, m), and a zigzag shape (n, O). Carbon nanotubes exhibit electrical characteristics such as semiconductors or metals according to their respective forms.

Graphene is a material in which carbon is connected to each other in a hexagonal shape to form a honeycomb two-dimensional planar structure. As shown in the drawing, electrons can flow through the xy axis, which is a two-dimensional plane, and thus has conductivity. As a non-conductive material.

Therefore, as shown in the drawing, when the two-dimensional plane of graphene is placed in parallel on the surface of the current collector, an electrode having polarization with respect to the ion-containing fullerene is made, and the graphene is present in the current collector as shown in the drawing. When the two-dimensional planes of the junction are perpendicular to each other, an electrode having polarity and conductivity with respect to the ion-containing fullerene is formed.

Fullerene can also bind fullerenes when irradiated with a laser. Figure 4a shows that the two fullerenes are combined, Figures 4b and 4c shows the combined in the x-y plane. Fullerenes in which two or more fullerenes are combined have different electrical conductivity depending on the coupling direction and the voltage applied thereto, thereby making it possible to make an electrode having only polarity or an electrode having both polarity and conductivity.

The fullerene may be bonded to the current collector by using the property that the fullerene is adsorbed on the surface of copper (Cu) or gold (Au). That is, when fullerene is placed on the Miller surface of copper (Cu) or gold (Au) having a Miller index, as shown in the drawing, gold (Cu) or copper (Cu) in which fullerene is used as a current collector It is adsorbed on to use it to form a fullerene electrode on the current collector. Separately, fullerene can also be bonded on a collector using a binder.

Meanwhile, in the supercapacitor of the present invention, a separator may be interposed between the first and second electrodes.

The separator according to the present invention preferably has high electron insulation, excellent wettability of the electrolyte solution, high ion permeability, and needs to be electrochemically stable within the range of applied voltage. The material of the separator is not particularly limited, but includes paper made of rayon or manila hemp; Polyolefin porous film; Polyethylene nonwovens; Polypropylene nonwovens etc. are used preferably. Furthermore, the present invention may be used as a separator, carbon nanotubes, fullerenes and the like.

Vacuum Chamber (12)

Vacuum chamber according to the present invention is to be formed of any one of silicon carbide, glass, quartz or plastic, non-ferrous metal, in the present invention, it is preferable to mold the vacuum chamber using silicon carbide.

The vacuum chamber of the present invention may be manufactured in a cylindrical, square, polygonal or other various shapes as well as in a geometric structure.

The supercapacitor of the present invention using the vacuum chamber comprises the steps of: forming a vacuum chamber with hydrocarbons; bonding a current collector to an inner surface of the vacuum chamber; forming an electrode on the current collector; Injecting the ion-encapsulated fullerene, the vacuum step and the sealing step.

In another embodiment, the present invention provides a method of forming a vacuum chamber with hydrocarbon or glass, installing a current collector on a base plate, forming a polarizable electrode on the current collector, and assembling the base plate to the vacuum chamber. And a current collector to be fitted into the vacuum chamber, thermally fusion bonding the base plate and the vacuum chamber, the vacuum step, and the sealing step.

On the other hand, the present invention has the characteristic that the anion and cation of the electrolyte injected during the vacuum operation to extract the air does not flow to the outside by interacting with each other. Therefore, the present invention can proceed with the vacuum naturally without the outflow of the electrolyte.

7 and 8 show an example of a vacuum chamber according to the present invention.

3 is a configuration in which an expansion pipe 14 is provided at an upper portion, and a bottleneck portion 16 is provided at a lower portion of the expansion pipe 14, and a vacuum pump is connected to the expansion pipe while air is formed in an electrode formed therein. Pull out, apply heat to the bottleneck after welding and seal by welding

As another example, the bottom surface is opened in the vacuum chamber of FIG. 3, the current collector and the electrode are formed through the opening of the bottom surface, and then heat-sealed and sealed with a bottom plate of the same material.

According to another embodiment of the present invention, as shown in FIG. 4, a vacuum member having an open bottom is provided, an electrode is accommodated using a base plate, and then the base plate and the vacuum member are heat-sealed.

For example, a base plate made of glass or the like is formed, and a positive electrode current collector and a negative electrode current collector are placed on the base plate to constitute it. A polarizable electrode is bonded to each of the positive electrode and the negative electrode current collector. In addition, ion-containing fullerene is injected into the electrode member.

In this state, the base plate is fitted to the bottom opening of the vacuum member, and the positive electrode collector and the negative electrode collector are positioned inside the vacuum chamber, and the base plate and the open portion are thermally fused. After the extraction through the expansion pipe provided in the base plate is to manufacture a supercapacitor.

On the other hand, the present invention has been described that the negative electrode and the positive electrode current collector is bonded or housed in the vacuum chamber, in some cases, the current collector and the electrode of several layers are put in the vacuum chamber in a coiled or concentric state Naturally, the current collector in the form of a plate and a plurality of electrodes may also be fitted.

Electrolyte

In the present invention, the electrolyte includes ion-containing fullerenes, in particular lithium-ion-full fullerenes.

Ion-containing fullerenes or salts thereof

The fullerene of the ion-encapsulated fullerene of the present invention is a pentagon of five carbons and a hexagon of six carbons combined in a spherical spherical shape to form a hollow, and various forms of fullerenes depending on the number of carbons used have. For example, fullerenes such as C60, C70, C72, C76, C78, C82, C84, C90, C94, and C96 are possible, but C60 consisting of 20 hexagons and 12 pentagons is best. The C60 is extremely stable physically and chemically by its structural characteristics, and has excellent mobility due to spherical symmetry, thereby improving stability and charge / discharge characteristics.

The ions contained in the C60 fullerene according to the present invention are preferably metal ions, especially alkali metal ions. These ions include lithium, sodium, potassium, cesium, magnesium, calcium, strontium, and the like. When fullerenes containing metal ions are charged by metal ions contained in fullerene, an electric field is applied between the two electrodes. It is easy to move. As fullerenes containing metal ions, Li ⁺ @ C 60 (where @ means an inclusion polymer), Li ⁺ @ C 70, Li ⁺ @ C 76 or Li ⁺ @ C 84 can be preferably used.

Further, the ion-containing fullerene salt ion containing-fullerene and ^{Cl -, Br -, F -} , I -, ClO 3 -, ClO 4 -, BF 4 -, A1Cl4 -, PF 6 -, SbC 16 - or SbF ₆ ^- Combined with at least one anion selected from the group consisting of. Such anions are more preferably ions having a diameter smaller than the size of the pores formed when the ion-containing fullerene or ion-containing fullerene salt is laminated. In this case, halogen is preferable, and F ⁻ is particularly preferable. In order to exchange corresponding ions, a generally known method may be used. For example, Li + @ C60] [PF 6 - a] [Li + @ C60] [ F - If you want to replace it with a] can be used a method generally known as shown in the following.

(Li + @ C60] [PF 6 -) + KF + 18-crown-6

(Li + @ C60] [F -) + (18-crown-6] K +) + PF 6 -]

Another method is to use an ion exchange resin.

On the other hand, the ion-containing fullerene of the present invention is made using the arc discharge method. Alternatively, energy may be supplied to ions to be implanted by using plasma generating means, and ion-encapsulated fullerenes may be produced by using the action of plasma and magnetic field.

In the present invention, a supercapacitor may be made using ionic inclusion fullerene, and a supercapacitor may also be made using ionic inclusion fullerene salt. The ion-containing fullerene salt may be subjected to, for example, cluster decomposition, removal of dissolved solids, precipitation, removal of generated salts, removal of empty fullerenes, extraction of atomic-containing fullerene cations, solid precipitation, solid recovery, crystallization, and recovery of crystals. To make.

The following describes the charging process of the vacuum hybrid supercapacitor according to the present invention.

When a voltage is applied to the vacuum hybrid supercapacitor of the present invention, an electric field is formed between the two electrodes 20 and 20 ', and the ion-containing fullerene 31 is moved toward the negative electrode 20 by the electric field. 32 is moved toward the positive electrode 20 'to form an electric double layer. At this time, the primary charging is performed by the ions contained in the ion-containing fullerene 31.

After the primary charging by the ions contained in the ion-encapsulated fullerene 31 is made, as shown in FIG. 1C, electrons 34 moved through the negative electrode current collector 10 are ionized through the negative electrode 20. Injected into the degenerate molecular orbital of the inner-encapsulated fullerene 31 is secondary charging by the molecular orbital of the ion-containing fullerene (31). Reference numeral 33 indicates a metal atom ion contained in the ion.

This will be described as follows.

There are five degenerate molecular orbits in fullerene, and each of these molecular orbits may contain one electron.

6 shows a cyclic voltammetry (CV) curve of lithium ion fullerene. As shown in the figure, reduction and oxidation of electrons are performed along the CV curve. That is, after the charge is made by entering electrons at each point indicated by the arrows ① to ⑤, the electrons are discharged one by one at the points indicated by the arrows ⑥ to ⑩.

Therefore, when power is applied to the hybrid supercapacitor of the present invention, first charging occurs by the ions 33 contained in the ion-encapsulated fullerene, and then secondary charging occurs by the molecular trajectory of the ion-encapsulated fullerene. Will charge.

In addition, the charged electrical energy is discharged through the reverse process.

At this time, since charging and discharging are performed in a vacuum atmosphere, not only has a very high charging voltage, but also has a very high discharge voltage.

In addition, since charging at a high voltage is possible, a very large amount of electric energy can be charged.

Hereinafter, the technical spirit of the present invention will be described in detail with reference to Examples.

In the description, the same or similar names and symbols are used for components having the same or similar components and functions.

<Example>

In this embodiment, copper (Cu) is used as the positive electrode current collector, aluminum (Al) is used as the negative electrode current collector, and activated carbon is bonded to the current collector to form a positive electrode and a negative electrode, and the activated carbon electrode is a halogen element. Doping the iodine (I3) will be described with an example that each electrode is configured to have both polarization and conductivity with respect to the ion-containing fullerene.

In addition, in this embodiment, C60 is used as the fullerene and lithium ion-containing fullerene (Li @ C60) in which lithium (Li) ions are injected into the C60 fullerene is described as an example.

In addition, embodiments of the present invention will be described by using an example of a non-aqueous electrolyte containing an electrolyte, the electrolyte is used for the ion-containing fullerenes, ionic liquid polymer, non-aqueous organic solvent, and halogen-substituted aromatic hydrocarbons as an example Will be explained.

The reason why the present embodiment is configured as described above is that other embodiments according to the spirit of the present invention can be easily understood from the present embodiment.

First, as shown in FIG. 1D, a vacuum chamber 40 is constructed, and current collectors 10 and 10 'are installed in the vacuum chamber 40, and a cathode current collector 10 made of aluminum and copper are used. After bonding the activated carbon on the positive electrode current collector 10 'with a binder, iodine, a halogen element, is doped to form electrodes 20 and 20' having polarity and conductivity.

Thereafter, the electrolyte is filled between the electrodes 20 and 20 'and then sealed with a case 40 to make a hybrid supercapacitor according to the present embodiment.

Hereinafter, the operational effects of the present embodiment will be described in detail.

FIG. 1A shows a discharge state. In the discharge state, lithium ion-containing fullerene 31 and anion 32 are randomly distributed as shown in the figure.

When the switch SW is turned on for charging, an electric field is formed between the negative electrode 10 and the positive electrode 10 ', and the positive electric charge fullerene 31 containing lithium ions is moved toward the negative electrode 10 by the electric field. In contact with the negative electrode 10. In this case, primary charging by lithium ions contained in the lithium ion-encapsulated fullerene 31 is performed.

After the primary charging by lithium ions contained in the lithium ion-encapsulated fullerene 31 is completed, secondary charging is performed by the degenerate molecular orbits present in the lithium ion-encapsulated fullerene 31.

This will be described as follows.

first. When the power is applied, the lithium ion-encapsulated fullerene 31 is moved to the negative electrode 20 by an electric field, and primary charging is performed by the polarization of lithium ions contained in the lithium-ion-encapsulated fullerene 31. At this time, the polarity of the negative electrode 20 is used.

Then, when the voltage gradually increases and a voltage higher than the reduction potential of the molecular orbital present in the lithium ion-containing fullerene 31 is applied, the electrons move sequentially as follows along the graph as shown in FIG. Will be made (① to ⑤). At this time, the conductivity of the negative electrode 20 'is used.

Li @ C60 <-> Li @ C60 ^- ¹ <-> Li @ C60 ^- ² <-> Li @ C60 ^- ³ <-> Li @ C60 ^- ⁴ <-> Li @ C60 ^-5

In addition, when lithium ions are contained in the fullerene hollow, the reduction potential with respect to the molecular orbital of the fullerene is lowered by 0.7 eV, thereby further improving charge and discharge efficiency.

At this time, the amount of charge to be charged is six times the amount of charge by the lithium ion. In addition, charging and discharging are performed using 1 nm C60 fullerene, which significantly increases the energy storage density. In addition, since it is not an energy storage using a chemical reaction, there is no energy loss and heat generation, and instant charging and instant discharge are possible. At this time, the charge and discharge characteristics can be controlled by controlling the components and the component ratio of the electrolyte solution.

On the other hand, when the switch (SW) is turned off, the discharge is made through the reverse process as when charging. That is, after the discharge is made along the path of ⑥ to 의 graph of FIG. 6, the charge charged by the lithium ions is also discharged. The above process is repeated to perform the discharge process.

However, in the above embodiment, the positive electrode and the negative electrode were made using activated carbon and then doped with a halogen element so as to have polarization and conductivity with respect to the ion-containing fullerene, but the technical spirit of the present invention is not limited thereto. In other words, the electrode can be configured to have polarity and conductivity such as graphene, carbon nanotubes, or fullerenes. Of course, it is possible to have different characteristics by changing the configuration of the positive electrode and the negative electrode. For example, it should be noted that one electrode may be configured to have good charging characteristics, and the other electrode may be configured to have good discharge characteristics.

In addition, in the above embodiment, the ion-containing fullerene is configured using C60 fullerene, but the technical spirit of the present invention is not limited thereto. In other words, fullerenes such as C60, C70, C72, C78, C82, C90, C94, and C96 may be used, as well as the fullerene salt may be used to configure the technical idea of the present invention.

10: negative electrode current collector 10 ': positive electrode current collector
20: negative electrode 20 ': positive electrode
30: electrolyte 31: ion-containing fullerene
32: anion 33: lithium ion
34: electronic 40: chamber

Claims (16)

As a supercapacitor having an electrode and an electrolyte,
Install the electrode inside the vacuum chamber,
The vacuum chamber is filled with an electrolyte containing a fullerene containing ions or a fullerene salt containing ions,
The charge is made by the ions contained in the fullerene,
Vacuum hybrid supercapacitor, characterized in that the filling by the fullerene itself. The vacuum hybrid supercapacitor of claim 1, wherein any one of the electrodes is configured to have polarity and conductivity with respect to the fullerene containing ions. The vacuum hybrid supercapacitor of claim 2, wherein the electrode having polarization with respect to the iontophorus fullerene is composed of activated carbon or Teflon. The method of claim 2, wherein the electrode having polarity with respect to the ion-containing fullerene is configured to have polarity with respect to the ion-containing fullerene by controlling the bonding direction of graphene, or by controlling the chirality of the carbon nanotubes. A vacuum hybrid supercapacitor, wherein the vacuum hybrid supercapacitor is configured to have polarity with respect to fullerene or to have polarization with respect to ion-containing fullerene by controlling the bonding direction of the fullerene. 3. The method of claim 2, wherein the electrode having polarity and conductivity with respect to the iontophorus fullerene is characterized in that the activated carbon is conductive by doping a halogen element to the activated carbon to have polarity and conductivity to the iontofullerene. Vacuum hybrid supercapacitors. According to claim 2, The electrode having polarity and conductivity with respect to the ion-containing fullerene, the ion-containing fullerene by controlling the bonding direction of the graphene or by controlling the bonding direction of the fullerene such that the graphene or fullerene is conductive A vacuum hybrid supercapacitor, characterized in that it has polarization and conductivity with respect to. 3. The method of claim 2, wherein the electrode having polarity and conductivity with respect to the ionpophore fullerene is controlled to have chirality of the carbon nanotubes so that the carbon nanotubes have conductivity so that they have polarity and conductivity with respect to the ionpofullerene. Vacuum hybrid supercapacitor, characterized in that. The vacuum hybrid supercapacitor according to claim 2, wherein the ionic inclusion fullerene is any one of a hetero atom contained in lithium, sodium, potassium, cesium, magnesium, calcium, and strontium. The vacuum hybrid supercapacitor of claim 2, wherein the atomic ions contained in the iontofullerene are a metal. 3. The vacuum hybrid supercapacitor according to claim 2, wherein the atomic ions contained in the iontofullerene are alkali metals. 3. The vacuum hybrid supercapacitor of claim 2, wherein the ion-containing fullerene is C60. The method of claim 2, wherein the ion-containing fullerene salt is Li ⁺ @ · ^- vacuum hybrid supercapacitor, characterized in that. The method of claim 2, wherein the ion corresponding to the valency of containing-fullerene is ^{Cl -, Br -, F -} , I -, ClO 3 -, ClO 4 -, BF 4 -, A1Cl4 -, PF 6 -, SbC 16 - or SbF ₆ ^- any one or two or more of the vacuum hybrid supercapacitors. The vacuum hybrid supercapacitor of claim 1, wherein the number of electrons charged in the degenerate molecular orbital of the iontophorus fullerene is 5 or less. The vacuum hybrid supercapacitor according to claim 1, wherein the charging potential is equal to or greater than the reduction potential of the iontofullerene. The vacuum hybrid supercapacitor of claim 1, wherein the vacuum chamber is formed of any one of hydrocarbon, glass, quartz, and synthetic resin.

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