KR20190110943A - Hybrid Supercapacitor - Google Patents

Abstract

Electrodes are made of a material having polarity and conductivity with respect to ion-containing fullerenes. An electrolyte containing the ion-containing fullerenes and ionic liquid polymers are filled between the electrodes. Then, charging is performed by applying a voltage higher than or equal to a reduction potential of the ion-containing fullerenes. First, primary charging is performed by means of the ionic liquid polymers, and secondary charging is performed by means of the ions contained in the ion-containing fullerenes. Second, tertiary charging is performed by means of the degenerated molecular trajectory of the ion-containing fullerenes. Thus, the energy storage capacity and energy storage density can be rapidly increased. The present invention enables the primary charging using the ionic liquid polymers, the secondary charging using the ions contained in the ion-containing fullerenes, and the tertiary 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, by using the fullerenes, which are nanoparticles, as the electrolyte, the energy storage density can be significantly increased, thereby making it possible to produce a compact and lightweight hybrid supercapacitor and increasing the charging and discharging characteristics. Further, by using physically and chemically very stable fullerenes, physically and chemically stable energy storage is possible.

Description

Hybrid Supercapacitor

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to hybrid supercapacitors that have dual charge characteristics, and in particular, fullerenes (hereinafter referred to as “ion-containing fullerenes”) containing ions and ionic liquid polymers as electrolytes. After the electrode is composed of a material having polarity and conductivity with respect to the ion-containing fullerene, charging is performed at a voltage equal to or lower than the reduction potential of the ion-containing fullerene. Secondary hybrid supercapacitors are used for secondary charging by ions contained in the iontofullerene, and secondly, for tertiary charging by degenerate molecular orbitals of the iontofullerene.

This invention has the advantage of dramatically improving the charging capacity, improving the charging and discharging characteristics, and 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.

An object of the present invention is to solve the above-mentioned conventional problems, in particular, after configuring a supercapacitor using an electrolyte containing ionic inclusion fullerene, so that the charge is made at a voltage higher than the reduction potential of the ion containing fullerene. By charging with the ions contained in the ion-containing fullerenes and by the ion-containing fullerenes themselves, the energy storage capacity and the energy storage density can be improved dramatically, and the physically and chemically extremely stable hybrid supercapacitors can be provided. It is for.

That is, the present invention forms an electrode with a material having polarity and conductivity with respect to the ion-containing fullerene, filling an electrolyte including the ion-containing fullerene between the electrodes, and then charging by applying a voltage higher than the reduction potential of the ion-containing fullerene. Thus, 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 reducing the energy storage capacity and the energy storage density. It's a big leap forward.

On the other hand, according to the present invention, after the supercapacitor is formed by using an electrolyte containing an ion-containing fullerene and an ionic liquid polymer, the charging is performed at a voltage higher than or equal to the reduction potential of the ion-containing fullerene, and thus the primary charging by the ionic liquid polymer. And secondary charging by ions contained in the ion-containing fullerene and tertiary charging by the ion-containing fullerene itself.

The present invention "hybrid supercapacitor" is a supercapacitor having an electrode and an electrolyte, the electrolyte comprises a fullerene containing ions, or a fullerene salt containing ions, to which an ionic liquid polymer is further added, It is characterized by the technical configuration that the primary filling is performed by the ionic liquid polymer, the secondary filling is performed by the ions contained in the fullerene, and the tertiary filling is performed by the fullerene itself.

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 polarization and conductivity.

In one aspect of the present invention, the electrode of any one of the cathode or the anode is made of carbon nanotubes, the carbon nanotubes contain an electrolyte containing a fullerene containing ions, or a fullerene salt containing ions, The non-aqueous electrolyte solution containing the electrolyte is filled.

In addition, the non-aqueous electrolyte solution (A) ion-containing fullerene or salts thereof; (B) an ionic liquid polymer; (C) a non-aqueous organic solvent; And (D) a halogen substituted aromatic hydrocarbon.

The fullerene according to the present invention is characterized in that the C60, the ion contained in the fullerene is characterized in that the metal ion, in particular alkali metal ion. Such ions include lithium, sodium, potassium, cesium, magnesium, calcium, strontium and the like.

The ion-containing fullerene salt ion containing-fullerene and Cl ^- configured ^{-, Br -, F -,} I -, ClO 3 -, ClO 4 -, BF 4 -, A1Cl4 -, PF 6 -, SbC 16 - or SbF ₆ It is characterized in that it can be used in combination with at least one anion selected from the group.

In the present invention, the "hybrid supercapacitor", in particular, uses an ion-containing fullerene and an ionic liquid polymer as an electrolyte, and constitutes an electrode with a material having polarization and conductivity with respect to the ion-containing fullerene, and then the reduction potential of the ion-containing fullerene. By charging at a voltage, the primary charging by the ionic liquid polymer, the secondary charging by ions contained in the ion-containing fullerene, and the third charging by the degenerate molecular trajectory of the ion-containing fullerene are performed. It works.

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 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,
7 is a schematic view showing one configuration according to an embodiment of the present invention;
8A is a schematic diagram showing a discharge state according to an embodiment of the present invention;
8B is a schematic diagram showing a state of charge in accordance with an embodiment of 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.

As shown in FIG. 1, the hybrid supercapacitor according to the present invention includes two electrodes 20 and 20 'respectively formed in the current collectors 10 and 10', and these electrodes 20 and 20 '. It consists of a non-aqueous electrolyte solution (30) filled between.

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.

That is, all of the electrodes of the hybrid supercapacitor of the present invention can be configured as electrodes having both polarization, polarization and conductivity, and can be configured differently according to circumstances. For example, one electrode may be configured to have polarity and conductivity with respect to ion-containing fullerene, and the other electrode may be configured to have polarity only. At this time, it is a matter of course that the material constituting each electrode can be different.

An electrode having polarity with respect to ion-containing fullerene is formed by bonding activated carbon or Teflon to a current collector using a binder, or bonding so that graphene and fullerene are polarized.

An electrode having polarity and conductivity with respect to ion-containing fullerene is formed by bonding an activated carbon, graphene, carbon nanotube, or fullerene to the current collector so as to have polarity and conductivity.

Porous activated carbon with polarity is made by carbonizing coconut fiber. When the activated carbon is bonded to the current collector using a binder, an electrode having polarization with respect to ion-containing fullerene is produced. Activated carbon having polarity and conductivity with respect to ion-containing fullerene is made by doping a polarized activated carbon with a halogen element such as iodine (I3). When the activated carbon is bonded to the current collector using a binder, an electrode having polarization and conductivity with respect to ion-containing fullerene is made.

Graphene is a material in which carbon is connected to each other in the form of a hexagon to form a honeycomb two-dimensional planar structure. As shown in FIG. 2A, electrons may flow through the xy axis, which is a two-dimensional plane, and thus has conductivity. As a non-conductive material. Therefore, as shown in FIG. 2B, bonding the graphene to the surface of the current collector so that the two-dimensional plane of graphene is placed in parallel creates an electrode having polarization with respect to ion-encapsulated fullerenes, as shown in FIG. 2C. When the two-dimensional plane of graphene is vertically bonded to the entire surface, an electrode having polarity and conductivity with respect to the ion-containing fullerene is formed.

Carbon nanotubes are hexagonal shapes consisting of six carbons connected to each other to form a tubular shape, and the diameter of the tube may be different depending on the synthetic conditions. In addition, as shown in FIG. 3, the chirality can be controlled to control the electrical characteristics, and the carbon nanotubes can be made to have only polarity with respect to the ion-containing fullerene, or to have both polarity and conductivity. have. 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.

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

Irradiation of fullerenes with lasers can bond fullerenes. 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 is preferably 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 the Miller index 111, as shown in FIG. 5, gold (Au) in which fullerene is used as the current collector or It is adsorbed to copper (Cu), which is used to form a fullerene electrode on the current collector. Separately, fullerene can also be bonded on a collector using a binder.

The hybrid supercapacitor of the present invention includes the current collector, the electrode bonded to the current collector, and the following non-aqueous electrolyte filled between the electrodes.

Non-aqueous electrolyte

In one aspect, the non-aqueous electrolyte of the present invention comprises (A) iontofullerene or a salt thereof; (B) an ionic liquid polymer; (C) a non-aqueous organic solvent; And (D) halogen-substituted aromatic hydrocarbons.

In another aspect, the present invention is (A) Ionpofullerene or a salt thereof; (C) a non-aqueous organic solvent; And (D) relates to a non-aqueous electrolyte containing a halogen-substituted aromatic hydrocarbon.

Furthermore, in the non-aqueous electrolyte solution of the present invention, an organic solvent and an ionic liquid may be optionally further added.

Hereinafter, the component of the non-aqueous electrolyte solution by this invention is demonstrated in detail.

(A) ion-containing fullerenes or salts thereof

In the present invention, the ion-containing fullerene corresponding to the electrolyte is intercalated by π-π interaction of halogen-substituted aromatic hydrocarbons, thereby maintaining the sustainability of charging and suppressing natural discharge.

This ion-containing fullerene is contained in the carbon nanotubes.

Fullerene is a pentagon of five carbons and a hexagon of six carbons combined in a spherical spherical shape to form a hollow. There are various types of fullerenes depending on the number of carbons used. 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 size of C60 including the electron cloud of C60 fullerene according to the present invention is 1.002nm, the main skeleton is 0.704nm, there is a space of 0.4nm diameter inside. Therefore, ions can be contained in this space.

Ion-containing fullerenes according to the present invention are 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.

(B) Ionic Liquid Polymer

In the ionic liquid polymer according to the present invention, the primary reaction is performed by reacting before the ion-containing fullerene during charging, followed by the secondary charging by the fullerene reaction.

The ionic liquid polymer may have the form of a dipole type (dual polymer), a cationic polymer, an anionic polymer, a copolymer or a polymer blend, preferably an anionic polymer. Is used, but is not limited thereto.

During charging, the polymer moves little and only the ion-containing fullerene moves, which is excellent in restoring (discharging) characteristics such as accumulating energy in the spring, and fast charging.

In the non-aqueous electrolyte solution of the present invention, the ionic liquid polymer may be 50 to 300 parts by weight, preferably 100 to 250 parts by weight, more preferably 90 to 120 parts by weight, more than 300 parts by weight based on 100 parts by weight of fullerene. If it is difficult to control the concentration, there is a problem in the case of less than 50 parts by weight of the filling reaction may not be made smoothly, the ratio of the ion phospho fullerene which is quite expensive is relatively high is not preferable.

The ionic liquid polymer according to the present invention has the advantages of being able to withstand a wide temperature change (-50 to 400 ° C.) as well as a pressure change, having the advantage of being able to withstand in a vacuum, and increasing the amount of dislocation.

It is preferably of the gel type or solid type, more preferably cationic polymer, anionic polymer or bipolar polymer.

In the present invention, the gel or solid type electrolyte can be used because the lithium ion-containing polymer is spherical symmetrical and can have high mobility even in the gel type electrolyte.

In the present invention, the ionic liquid polymer is Cl and the cationic polymer of the formula (1) or the formula _{^{2 -, Br -, BF 4}} -, PF 6 -, (CF 3 SO 2) 2 N -, HPO 3 R 11- ( where , R ¹¹ is a C ₁ ~ C ₆ alkyl group) and COOH ^- may be used a cationic ion polymer having one or more anions selected from the group consisting of.

[Formula 1]

[Formula 2]

R in formulas 1 and 2 is a hydrogen atom, alkyl, cycloalkyl, allyl, aryl or alkylaryl, wherein alkyl is C ₁ -C ₆ , cycloalkyl is C ₃ -C ₁₀ , allyl is C ₂ -C _20, Aryl is C ₆ -C ₂₀ and n is an integer from 5,000 to 30,000.

In addition, the ionic liquid polymer is an anionic polymer of formula 6 and R ₄ -P ⁺ (where R is a hydrogen atom, alkyl, cycloalkyl, allyl, aryl or alkylaryl, wherein alkyl is C ₁ -C ₆ , Cycloalkyl may be C ₃ -C ₁₀ , allyl is C ₂ -C _{20, and} aryl is C ₆ -C ₂₀ .

[Formula 3]

N in the formula (3) is an integer of 5,000 to 500,000.

In addition, the ionic liquid polymer may be a dual polymer of formula (4).

[Formula 4]

In formula 4 A ^- is a SO ₃ ^- or PO ₃ H ^- or CO ₂ ^-, n is an integer of from 5,000 to 300,000.

(C) non-aqueous organic solvent

In the electrolyte according to the present invention, the non-aqueous organic solvent serves to suppress internal resistance.

The non-aqueous organic solvent may be a cyclic carbonate, a chain carbonate or a mixture of a cyclic carbonate and a chain carbonate. Preferably, the cyclic carbonate is the cyclic carbonate is ethyl carbonate (EC). Selected from the group consisting of propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), γ-butyrolactone, and mixtures thereof It may be one or more carbonates, preferably ethylene carbonate or propylene carbonate.

Examples of the chain carbonate used in the present invention include dimethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, n-butyl methyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl propyl carbonate, ethyl isopropyl carbonate, dipropyl carbonate and fluorodimethyl. Carbonate, difluorodimethyl carbonate, trifluoro dimethyl carbonate, tetrafluoro dimethyl carbonate, fluoro dimethyl carbonate, fluoroethyl methyl carbonate, difluoro ethyl methyl carbonate, trifluoro ethyl methyl carbonate, methyl acetate, ethyl acetate Methyl propionate, methyl fluoroacetate, methyl difluoroacetic acid, methyl trifluoroacetic acid, ethyl fluoroacetic acid, ethyl difluoroacetic acid, ethyl trifluoroacetic acid, methyl fluoropropionate Methyl uropropionate, methyl trifluoropropionate, or mixtures thereof.

(D) halogen substituted aromatic hydrocarbons

In the electrolyte solution of the present invention, the halogen-substituted aromatic hydrocarbons do not have intercalation in the electrolyte, and power density is generated by the dipole moment between carbon and halogen atoms, and internal resistance is generated.

That is, in the present invention, the filling is performed by first reacting the dipole moment of the solvent in the electric field, and the filling is performed by the ion-containing fullerene in the second order. Π-π bonds formed in an instant are charged by dipoles, and then ion-containing fullerenes are moved and charged. At the time of discharge, it discharges first by the dipole moment of a solvent, and then discharges by ion-containing fullerene. Since the two charges proceed in this way, there is an effect that the power density is increased as a result.

Intercalation solves the problems of existing EDLCs, namely small capacity and short duration. Intercalation occurs by π-π interactions and occurs at carbonaceous electrodes with π electrons.

In the present invention, the ionic liquid polymer may be 0.5 to 50 parts by weight, and the ion-containing fullerene may be added to 0.5 to 50 parts by weight based on 100 parts by weight of the mixed weight of the non-aqueous organic solvent and the halogen-substituted aromatic hydrocarbon. .

In the present invention, the weight ratio of the non-aqueous organic solvent and the halogen-substituted aromatic hydrocarbon may be 1: 0.5 to 5, preferably 1: 1 to 5, most preferably 1: 1. When the weight ratio is less than 1: 0.5, there is a problem that it is difficult to control the internal resistance, and when it exceeds 1: 5, there is a problem that the concentration control is difficult.

In the present invention, the halogen-substituted aromatic hydrocarbon chloronaphthalene and the organic solvent propylene carbonate are mixed in a 1: 1 ratio.

In the present invention, the halogen substituted aromatic hydrocarbon is preferably selected from the group consisting of halogen substituted benzene, halogen substituted naphthalene and halogen substituted anthracene. Halogen is F, Cl, Br or I.

The halogen substituted benzene may be represented by the formula (1).

[Formula 5]

In formula 1 R ¹ to R ⁶ each independently are a C ₁ ~ C ₆ alkyl group, a halogen or a C ₁ ~ C ₆ substituted with a halogen atom alkilgiyi unsubstituted, are necessarily substituted with one or more halogen.

The halogen substituted naphthalene may be represented by the formula (6).

[Formula 6]

In Formula 2 R ¹ to R ⁸ each independently are a C ₁ ~ C ₆ alkyl group, a halogen or a C ₁ ~ C ₆ substituted with a halogen atom alkilgiyi unsubstituted, are necessarily substituted with one or more halogen.

The halogen substituted anthracene may be represented by the formula (7).

[Formula 7]

In Formula 3 R ¹ to R ¹⁰ are each independently selected from unsubstituted C ₁ ~ C ₆ alkyl group, a halogen or a halogen atom being substituted with C ₁ ~ C ₆ alkilgiyi, and be substituted one or more halogen.

Preferably monohalo-benzene, dihalo-benzene, trihalo-benzene, monohalo-naphatalene, dihalo-benzene (diharo-naphatalene) or trihalo-naphatalene can be used, more preferably chlorobenzene, 1,2-chlorochloro, 1,2-3 -Trichlorobenzene (1,2-3-trichlorobenzene), 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene), chloronaphthalene, 1-chloronaphatalene, 1 One or a mixture of 1-fluoronaphatalene may be used.

In the electrolyte solution of the present invention, the halogen-substituted aromatic hydrocarbons increase the internal resistance, while the non-aqueous electrolyte solution lowers the internal resistance. Thus, the charge and discharge characteristics can be controlled by controlling the internal resistance. By controlling the proportion of halogen-substituted aromatic hydrocarbons that determine solubility, the agglomerate fullerenes are prevented from agglomerating and efficient filling is achieved.

In the present invention, the non-aqueous electrolyte solution is a 1: 1 mixture of the non-aqueous organic solvent and the halogen-substituted aromatic hydrocarbon, 0.1 to 80 parts by weight, preferably 0.1 to 50 parts by weight, More preferably, it may be 5 to 20 parts by weight.

Even if the amount of ion-containing fullerenes is 0.1 parts by weight or less, a sufficient amount of filling can be secured, but it is difficult to control the concentration of the electrolyte at 0.1 parts by weight or less. have.

In the present invention, the non-aqueous electrolytic solution is a 1: 1 mixture of the non-aqueous organic solvent and the halogen-substituted aromatic hydrocarbon, and 0.1 to 50 parts by weight of the ionic pore fullerene and 1 to 50 parts by weight of the ionic liquid polymer are further added to the mixture. May be included.

Meanwhile, the electrolyte according to the present invention may further include an ionic liquid and an organic solvent. As one example of this,

In ionic liquid,

1- (2-hydroxyethyl) -3-methylimidazolium tetrafluoroborate (1- (2-Hydroxyethyl) -3-methylimidazolium tetrafluoroborate)

1- (2-hydroxyethyl) -3-methylimidazolium tris (pentafluoroethylsulfonyl) trifluoro phosphate (1- (2-Methoxyethyl) -1-methylpyrrolidinium tris (pentafluoroethyl) trifluorophosphate)

1- (3-cyanopropyl) -3-methylimidazolium chloride purum (1- (3-Cyanopropyl) -3-methylimidazolium chloride purum)

1- (3-cyanopropyl) -3-methylimidazolium dicyamide (1- (3-Cyanopropyl) -3-methylimidazolium dicyanamide)

1- (3-cyanopropyl) -3-methylimidazolium bis (trifluoromethylsulfonyl) imide (1- (3-Cyanopropyl) -3-methylimidazoliumbis- (trifluormethylsulfonyl) imid)

1- (3-cyanopropyl) pyridinium bis (1- (3-Cyanopropyl) pyridinium bis (trifluoromethylsulfonyl) imide)

1- (3-cyanopropyl) pyridinium chloride (1- (3-Cyanopropyl) pyridinium chloride)

1- (Cyanomethyl)-3-methylimidazolium chloride (1- (Cyanomethyl) -3-methylimidazolium chloride)

1,2,3-trimethylimidazolium chloride (1,2,3-Trimethylimidazolium chloride)

1,2,3-trimethylimidazolium methylsulfate (1,2,3-Trimethylimidazolium methylsulfate)

1,2,4-trimethylimidazolium methylsulfate (1,2,4-Trimethylpyrazolium methylsulfate)

1,2-dimethyl-3-propylimidazolium bis (trifluoromethylsulfonyl) -imide (1,2-Dimethyl-3-propylimidazolium bis (trifluoromethylsulfonyl) -imide)

1,2-dimethyl-3-propylimidazolium tris (trifluoromethylsulfonyl)-methide (1,2-Dimethyl-3-propylimidazolium tris (trifluoromethylsulfonyl) -methide)

1,3-bis (3-cyanopropyl) imidazolium bis (trifluoromethylsulfonyl) imide (1,3-Bis (3-cyanopropyl) imidazolium bis (trifluoromethylsulfonyl) imide)

1,3-bis (3-cyanopropyl) imidazolium chloride (1,3-Bis (3-cyanopropyl) imidazolium chloride)

1,3-bis (cyanopropyl) imidazolium bis (trifluoromethylsulfonyl) imide (1,3-Bis (cyanomethyl) imidazolium bis (trifluoromethylsulfonyl) imide)

1,3-bis (cyanopropyl) imidazolium chloride (1,3-Bis (cyanomethyl) imidazolium chloride)

1,3-Dibutylimidazolium chloride

1,3-Dibutylimidazolium tetrachloroaluminate

1,3-Dimethylimidazolium chloride

1,3-Dimethylimidazolium dimethylphosphate

1,3-Dimethylimidazolium hydrogencarbonate

1,3-dimethylimidazolium iodine (1,3-Dimethylimidazolium iodide)

1,3-Dimethylimidazolium tetrachloroaluminate

1,4-Dibutyl-3-phenylimidazolium bis (trifluoromethylsulfonyl) amide (1,4-Dibutyl-3-phenylimidazoliumbis [trifluoromethylsulfonyl] amide)

1-Butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (1-Butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide)

1-Butyl-1-methylpyrrolidinium methylcarbonate

1-Butyl-1-methylpyrrolidinium tetracyanoborate

1-Butyl-1-methylpyrrolidinium tris (pentafluoroethyl) trifluoro phosphate (1-Butyl-1-methylpyrrolidinium tris (pentafluoroethyl) trifluorophosphate)

1-butyl-2,3-dimethylimidazolium chloride (1-Butyl-2,3-dimethylimidazolium chloride)

1-butyl-2,3-dimethylimidazolium iodine (1-Butyl-2,3-dimethylimidazolium iodide)

1-Butyl-2,3-dimethylimidazolium trifluoromethanesulfonate

1-butyl-2,3-methylimidazolium bis (trifluoromethylsulfonyl) imide (1-Butyl-2,3-methylimidazolium bis (trifluoromethylsulfonyl) imide)

1-Butyl-3-methylimidazolium 2- (2methoxyethoxy) methyl sulfate (1-Butyl-3-methylimidazolium 2- (2methoxyethoxy) ethyl sulfate)

1-Butyl-3-methylimidazolium acetate

1-Butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (1-Butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide)

1-Butyl-3-methylimidazolium bromide

1-Butyl-3-methylimidazolium chloride

1-butyl-3-methylimidazolium dibutylphosphate (1-Butyl-3-methylimidazolium dibutylphosphate)

1-Butyl-3-methylimidazolium dicyanamide

1-Butyl-3-methylimidazolium heptachlorodialuminate (1-Butyl-3-methylimidazolium heptachlorodialuminate)

1-Butyl-3-methylimidazolium hexafluorophosphate (1-Butyl-3-methylimidazolium hexafluorophosphate)

1-Butyl-3-methylimidazolium hydrogencarbonate

1-Butyl-3-methylimidazolium hydrogensulfate (1-Butyl-3-methylimidazolium hydrogensulfate)

1-Butyl-3-methylimidazolium iodine (1-Butyl-3-methylimidazolium iodide)

1-Butyl-3-methylimidazolium methanesulfonate

1-Butyl-3-methylimidazolium methyl sulfate

1-Butyl-3-methylimidazolium nitrate

1-butyl-3-methylimidazolium octylsulfate (1-Butyl-3-methylimidazolium octylsulfate)

1-Butyl-3-methylimidazolium tetrachloroaluminate

1-Butyl-3-methylimidazolium tetrachloroferrate

1-Butyl-3-methylimidazolium tetrafluoroborate

1-Butyl-3-methylimidazolium thiocyanate (1-Butyl-3-methylimidazolium thiocyanate)

1-Butyl-3-methylimidazolium trifluoromethanesulfonate

1-Butyl-3-methylimidazolium triiodide

1-Butyl-3-methylimidazolium tris (pentafluoroethylsulfonyl) trifluorophosphate (1-Butyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate)

1-Butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide (1-Butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide)

1-Butylpyridinium bis (trifluoromethylsulfonyl) imide

1-decyl-3-methylimidazolium chloride (1-Decyl-3-methylimidazolium chloride)

1-Dodecyl-3-methylimidazolium chloride

1-Ethyl-1-methylpiperidinium methylcarbonate

1-Ethyl-2,3-dimethylimidazolium bis (pentafluoroethylsulfonyl) imide (1-Ethyl-2,3-dimethylimidazolium bis (pentafluoroethylsulfonyl) imide)

1-Ethyl-2,3-dimethylimidazolium bromide

1-ethyl-2,3-dimethylimidazolium chloride (1-Ethyl-2,3-dimethylimidazolium chloride)

1-Ethyl-2,3-dimethylimidazolium methylsulfate

1-ethyl-2,3-dimethylimidazolium hexafluorophosphate (1-Ethyl-2,3-dimethylimidazolium hexafluorophosphate)

1-Ethyl-2,3-dimethylimidazolium methylcarbonate

1-ethyl-3-methyl-1H-imidazolium tetrafluoroborate (1-Ethyl-3-methyl-1H-imidazolium tetrafluoroborate)

1-ethyl-3-methylimidazolium 2 (2-methoxyethoxy) ethylsulfate (1-Ethyl-3-methylimidazolium 2 (2-methoxyethoxy) ethylsulfate)

1-Ethyl-3-methylimidazolium acetate

1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) imide) (1-Ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) imide)

1-Ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (1-Ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide)

1-Ethyl-3-methylimidazolium bromide

1-Ethyl-3-methylimidazolium chloride

1-Ethyl-3-methylimidazolium dibutylphosphate (1-Ethyl-3-methylimidazolium dibutylphosphate)

1-Ethyl-3-methylimidazolium dicyanamide

1-Ethyl-3-methylimidazolium diethylphosphate

1-ethyl-3-methylimidazolium ethylsulfate (1-Ethyl-3-methylimidazolium ethylsulfate)

1-ethyl-3-methylimidazolium hexafluoroarsenate (1-Ethyl-3-methylimidazolium hexafluoroarsenate)

1-Ethyl-3-methylimidazolium hydrogencarbonate

1-Ethyl-3-methylimidazolium hydrogensulfate (1-Ethyl-3-methylimidazolium hydrogensulfate)

1-Ethyl-3-methylimidazolium iodine (1-Ethyl-3-methylimidazolium iodide)

1-Ethyl-3-methylimidazolium methanesulfonate

1-Ethyl-3-methylimidazolium nitrate (1-Ethyl-3-methylimidazolium nitrate)

1-ethyl-3-methylimidazolium octylsulfate (1-Ethyl-3-methylimidazolium octylsulfate)

1-ethyl-3-methylimidazolium tetrabromoaluminate (III) (1-Ethyl-3-methylimidazolium tetrabromoaluminate (III))

1-Ethyl-3-methylimidazolium tetrachloroaluminate

1-Ethyl-3-methylimidazolium tetrachlorogallate

1-Ethyl-3-methylimidazolium tetracyanoborate

1-Ethyl-3-methylimidazolium tetrafluoroborate

1-ethyl-3-methylimidazolium thiocyanate (1-Ethyl-3-methylimidazolium thiocyanate)

1-ethyl-3-methylimidazolium trifluoromethanesulfonate (1-Ethyl-3-methylimidazolium trifluoromethanesulfonate)

1-Ethyl-3-methylimidazolium triiodide

1-ethyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate (1-Ethyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate)

1-Ethyl-3-methylimidazolium tris (trifluoromethylsulfonyl) mesdeide (1-Ethyl-3-methylimidazolium tris (trifluoromethylsulfonyl) methide)

1-hexyl-1-methyl-pyrrolidinium tetracyanoborate

1-hexyl-3-methyl methylimidazolium bis (trifluoromethylsulfonyl) imide (1-Hexyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide)

1-hexyl-3-methylimidazolium chloride (1-Hexyl-3-methylimidazolium chloride)

1-hexyl-3-methyl methylimidazolium hexafluorophosphate (1-Hexyl-3-methylimidazolium hexafluorophosphate)

1-hexyl-3-methyl imidazolium tetracyanoborate (1-Hexyl-3-methylimidazolium tetracyanoborate)

1-hexyl-3-methyl imidazolium trifluoromethylsulfonyl (1-Hexyl-3-methylimidazolium trifluormethylsulfonat)

1-hexyl-3-methyl methylimidazolium tris (pentafluoroethyl) trifluorophosphate (1-Hexyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate)

1-hexyloxymethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (1-Hexyloxymethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide)

1-hexyloxymethyl-3-methylimidazolium tetrafluoroborate

1-i-propyl-3-methyl-imidazolium bis (trifluoromethylsulfonyl) imide (1-i-Propyl-3-methyl-imidazolium bis (trifluoromethylsulfonyl) imide)

1-i-propyl-3-methylimidazolium iodine (1-i-Propyl-3-methylimidazolium iodide)

1-i-propyl-3-methyl-imidazolium-hexafluorophosphate (1-i-Propyl-3-methyl-imidazolium-hexafluorophosphate)

1-Methyl-3-methyl-imidazolium dimethylphosphate

1-Methyl-3-methyl-imidazolium methylsulfate

1-Methyl-3-propylimidazolium chloride

1-methyl-4-octylpyridinium bromide (1-Methyl-4-octylpyridinium bromide)

1-methyl-4-octylpyridinium colloid (1-Methyl-4-octylpyridinium chloride)

1-Methyl-4-octylpyridinium iodine (1-Methyl-4-octylpyridinium iodide)

1-Methylimidazolium chloride

1-Methylimidazolium hydrogensulfate

1-n-butyl-3-methylimidazolium bromide (1-n-Butyl-3-methylimidazolium Bromide)

1-n-butyl-3-methylimidazolium chloride (1-n-Butyl-3-methylimidazolium Chloride)

1-n-butyl-3-methylimidazolium hexafluorophosphate (1-n-Butyl-3-methylimidazolium Hexafluorophosphate)

1-n-butyl-3-methylimidazolium tetrafluoroborate (1-n-Butyl-3-methylimidazolium Tetrafluoroborate)

1-n-Butyl-3-methylimidazolium trifluoromethanesulfonate

1-n-heptyl-3-methylimidazolium hexafluorophosphate (1-n-Heptyl-3-methylimidazolium hexafluorophosphate)

1-n-octyl-3-methylimidazolium hexafluorophosphate (1-n-Octyl-3-methylimidazolium hexafluorophosphate)

1-n-octyl-3-methylimidazolium tetrafluoroborate (1-n-Octyl-3-methylimidazolium tetrafluoroborate)

1-n-pentyl-3-methylimidazolium hexafluorophosphate (1-n-Pentyl-3-methylimidazolium hexafluorophosphate)

1-n-propyl-2,3-dimethylimidazolium bis (pentafluoroethylsulfonyl) amide (1-n-Propyl-2,3-dimethylimidazolium bis (pentafluoroethylsulfonyl) imide)

1-Octyl-3-methylimidazolium chloride (1-Octyl-3-methylimidazolium chloride)

1-octyl-3-methylimidazolium trifluoromethylsulfonyl (1-Octyl-3-methylimidazolium trifluormethylsulfonat)

1-propyl-2,3-dimethylimidazolium chloride (1-Propyl-2,3-dimethylimidazolium chloride)

1-propyl-2,3-dimethylimidazolium hexafluorophosphate (1-Propyl-2,3-dimethylimidazolium hexafluorophosphate)

1-propyl-3-methylimidazolium tetrachloroaluminate (1-Propyl-3-methylimidazolium tetrachloroaluminate)

1-vinyl-3-methylimidazolium hydrogencarbonate

2,3 Dimethyl-1-propylimidazolium bis (trifluoromethylsulfonyl) imide (2,3 Dimethyl-1-propylimidazolium bis (trifluormethylsulfonyl) imide)

2,3 Dimethyl-1-propylimidazolium iodine (2,3 Dimethyl-1-propylimidazolium iodide)

2,3-Dimethyl-1-n-propylimidazolium bis (trifluoromethylsulfonyl) imide (2,3-Dimethyl-1-n-propylimidazolium bis (trifluoromethylsulfonyl) imide)

2,4,5-trimethylimidazolium chloride (2,4,5-Trimethylimidazolium chloride)

2-Hydroxyethyltrimethylammonium acetate

2-Hydroxyethyl-trimethylammonium dimethylphosphate

3-Methyl-1-propylimidazolium bis (trifluoromethylsulfonyl) imide)

3-Methyl-1-propylimidazolium iodine (3-Methyl-1-propylimidazolium iodide)

3-Methyl-1-propylimidazolium bis (trifluoromethylsulfonyl) imide (3-Methyl-1-propylpyridinium bis (trifluoromethylsulfonyl) imide)

4-Ethyl-4-methylmorpholinium methylcarbonate

4-Methyl-N-butylpyridinium tetrafluoroborate

Ethyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate

Ethyldimethyl- (2-methoxyethyl) ammonium tris (pentafluoroethyl) trifluorophosphat) Ethyldimethyl- (2-methoxyethyl) ammonium bis (pentafluoroethyl) trifluorophosphate

Ethyl-dimethyl-propylammonium bis (trifluoromethylsulfonyl) imide

Methyltrioctylammonium thiosalicylate

N- (methoxyethyl) -1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (N- (Methoxyethyl) -1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide

N, N-dimethylpyrrolidinium bis (trifluoromethylsulfonyl) imide

N, N-Dimethylpyrrolidinium Iodide

N-Butyl-1-methylpyrrolidinium (trifluoromethylsulfonyl) imide)

N-Butyl-1-methylpyrrolidinium bis [oxalato (2-)-O, O '] borate

N-Butyl-1-methylpyrrolidinium bromide

N-Butyl-1-methylpyrrolidinium chloride

N-Butyl-1-methylpyrrolidinium dicyanamide

N-Butyl-1-methylpyrrolidinium trifluoromethanesulfonate

N-Butyl-1-methylpyrrolidinium tris (pentafluoroethyl) trifluorophosphate (N-Butyl-1-methylpyrrolidinium tris (pentafluoroethyl) trifluorophosphate)

N-Butyl-4- (N ', N'-dimethylammonium) pyridinium bis (trifluoromethylsulfonyl) imide (N-Butyl-4- (N', N'-dimethylammonium) pyridinium bis (trifluoromethylsulfonyl) imide)

N-Butylpyridinium chloride

N-Butylpyridinium tetrafluoroborate

N-Ethyl-3-methylpyridinium ethylsulfate

N-Ethyl-3-methylpyridinium perfluorobutanesulfonate

N-butyl-4- (N ', N'-dimethylammonium) pyridinium bis (trifluoromethylsulfonyl) imide (N-Ethyl-4- (N', N'-dimethylammonium) pyridinium bis (trifluoromethylsulfonyl) imide)

N-ethyl-N, N-dimethyl-2-methoxyethyl ammonium tris (pentafluoroethyl) trifluorophosphate (N-Ethyl-N, N-dimethyl-2-methoxyethyl ammonium tris (pentafluoroethyl) trifluorophosphate)

N-ethylpyridinium bis (trifluoromethylsulfonyl) imide

N-hexyl-4- (N ', N'-dimethylammonium) pyridinium bis (trifluoromethylsulfonyl) imide

N-Hexyl-4- (N ', N'-dimethylammonium) pyridinium bis (trifluoromethylsulfonyl) imide

N-Methyl-N-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide

N-Methyl-Nn-propylpyrrolidinium bis (trifluoromethylsulfonyl) imide

Pentamididazolium (trifluoromethylsulfonyl) imide

Pentamididazolium hexafluorophosphate (Pentamethylimidazolium hexafluorophosphate)

Pentamididazolium Iodide (Pentamethylimidazolium iodide)

Pyridinium ethoxyethylsulfate

Tetrabutylammonium chloride

Tetrabutylammonium bis (pentafluoroethylsulfonyl) imide)

Tetrabutylammonium bis (trifluoromethylsulfonyl) imide)

Tetrabutylammonium hexafluorophosphate

Tetrabutylammonium tetrafluoroborate

Tetrabutylammonium tris (trifluoromethylsulfonyl) methide

Tetrabutylammonium Perchlorate (Tetrahexylammonium perchlorate)

Tetra-iso-pentylammonium iodide

Tetramethylammonium tris (pentafluoroethyl) trifluorophosphate

Tetra-N-butylammonium 4-toluenesulfonate

Tetra-N-butylammonium benzenesulfonate

Tetra-n-butylammonium bis (trifluoromethylsulfonyl) imide

Tetra-N-butylammonium bromide

Tetra-N-butylammonium butanesulfonate

Tetra-N-butylammonium ethanesulfonate

Tetra-N-butylammonium methanesulfonate

Tetra-N-butylammonium nitrate

Tetra-N-butylammonium nitrite

Tetra-N-butylammonium octanesulfonate

Tetra-N-butylammonium pentacyanopropenide

Tetra-N-butylammonium pentafluoroenzenesulfonate

Tetra-N-butylammonium picrate

Tetra-N-butylammonium sulfamate

Tetra-N-butylammonium tetra-N-butylborate

Tetra-N-butylammonium thiocyanate

Tetra-N-butylammonium trifluoromethanesulfonate

Tetra-n-butylammonium tris (trifluoromethylsulfonyl) methide)

Tetra-N-butylammoniumiodide

Tetra-N-heptylammoniumiodide

Tetra-N-hexylammoniumbromide

Tetra-N-hexylammoniumiodide

Tetra-N-hexylammonium tetrafluoroborate

Tetra-N-pentylammoniumiodide

Tetra-N-pentylammonium nitrate

Tetra-N-pentylammonium thiocyanate

Tetrapentylammonium bromide

Tributylmethylammonium methylcarbonate

Tributylmethylammonium methylsulfate

Tributylmethylphosphonium dibutylphosphate

Tributylmethylphosphonium methylcarbonate

Triethylamine hydrochloride 2 AlCl3]

Triethylmethylammonium dibutylphosphate

Triethylmethylammonium Methylcarbonate

Triethylmethylphosphonium dibutylphosphate

Tri-N-butylmethylammonium butanesulfonate

Tri-N-butylmethylammonium octanesulfonate

Tri-N-butylmethylammonium perfluorobutanesulfonate

Tri-N-butylmethylammonium perfluorooctanesulfonate

Tri-n-hexyl-n-tetradecylphosphonium chloride

Trioctylmethylammonium thiosalicylate

Tri (2-hydroxyethyl) methylammonium methylsulfate (Tris (2-hydroxyethyl) methylammonium methylsulfate),

As an organic solvent,

1,1,1,3,3,3-hexafluoro-2-propanol (1,1,1,3,3,3-hexafluoro-2-propanol)

1,1,1-trichloroethane

1,1,2,2-tetrachloroethane (1,1,2,2-tetrachloroethane)

1,1,2-trichlorotrifluoroethane

1,2,3,5-tetramethylbenzene (1,2,3,5-tetramethylbenzene)

1,2-butanediol (1,2-butanediol)

1,2-dichlorobenzene

1,2-dichloroethane

1,2-dimethoxybenzene (veratrole)

1,2-dimethoxyethane (monoglyme)

1,2-propanediol (1,2-propanediol)

1,3-butanediol

1,3-dioxolane (1,3-dioxolane)

1,3-propanediol

1,4-butanediol (1,4-butanediol)

1,4-dimethylpiperazine (1,4-dimethylpiperazine)

1,4-dioxane (1,4-dioxane)

1-butanol

1-chlorobutane

1-decanol

1-hexanol

1-methyltaphthalin (1-methylnaphthalene)

1-methylpiperidine

1-methylpyrrole

1-methylpyrrolidin-2-one (1-methylpyrrolidin-2-one)

1-methylpyrrolidine

1-nonanol

1-octanol

1-pentanol

1-propanol

1-undecanol

2,2,2-trichloroethanol

2,2,2-trifluoroethanol

2,2,3,3-tetrafluoro-1-propanol

2,2,3,4,4,4-hexafluoro-1-butanol (2,2,3,4,4,4-hexafluoro-1-butanol)

2,2,4-trimethylpentane

2,3-butanediol

2,4,6-trimethylpyridine

2,6-dimethylpyridine

2-butanol

2-butanone

2-butoxyethanol

2-chloroethanol

2-hexanol

2-methoxyethanol

2-methoxyethylether (diglyme)

2-methyl-1,3-propanediol

2-methyl-1-butanol

2-methyl-1-pentanol

2-methyl-1-propanol

2-methyl-2-butanol

2-methyl-2-propanol

2-methylbutane

2-methylbutiric acid

2-methylfuran

2-methylpyridine

2-methyltetrahydrofuran

2-octanol

2-pentanol

2-pentanone

2-phenylethanol

2-propanol

2-pyrrolidinone

3,5,5-trimethyl-2-cyclohexenone (isophorone) (3,5,5-trimethyl-2-cyclohexenone (isophorone)

3-hexanol

3-methyl-1-butanol

3-methyl-2-butanol

3-pentanol

3-pentanone

4-methyl-2-pentanone (4-methyl-2-pentanone)

Acetic acid

Acetone

Acetonitrile

Acetophenone

Allyl alcohol (2-propenol)

Anisol (methyl phenyl ether)

Benzene

Benzonitrile

Benzyl alcohol

Bromobenzene

Butyronitrile

Carbon disulfide

Chloroacetonitrile

Chlorobenzene

Chloroform

Cineole

Cis-decaline

Cycloheptane

Cycloheptanol

Cyclohexane

Cyclohexanol

Cyclohexanone

Cyclohexylamine

Cyclooctane

Cyclooctanol

Cyclopentane

Cyclopentanol

Cyclopentanone

Decaline

Decane

Dibenzyl ether

Dichloroacetic acid

Dichloromethane

Diethyl ether

Diisopropyl ether

Dimethoxymethane

Dimethyl carbonate

Dimethyl sulphite

Dimethyl sulfoxide

Di-n-butyl ether

Di-n-butyl oxalate

Di-n-butylamine

Di-n-hexyl ether

Di-n-pentyl ether

Di-n-propyl ether

Dodecane

Ethanol

Ethyl 2-methoxy acetate

Ethyl acetate

Ethyl benzoate

Ethyl salicylate

Ethylbenzene

Ethylcyclohexane

Ethylene glycol (1,2-ethanediol)

Ethylenediamine

Fluorobenzene

Formamide

Formic acid

Furan

Gas

g-butyrolactone

Glycerol (glycerol (1,2,3-propanetriol))

Heptane

Heptanoic acid

Hexadecane

Hexafluorobenzene

Hexane

Hexanoic acid

Hexamethylphosphoric acid triamide (HMPA)

Iodobenzene

Ethyl iodide

Isoamyl acetate

Isobutiric acid

Isobutyronitrile

Isovaleric acid

m-cresol

Mesitylene

Methanol

Methyl acetate

Methyl benzoate

Methyl formate

Methyl salicylate

Methylcyclohexane

Methylene chloride

Morpholine

m-xylene

N, N'-dimethylpropyleneurea

N, N-dimethylacetamide (N, N-diethylacetamide)

N, N-diethylformamide

N, N-dimethylacetamide

N, N-dimethylaniline

N, N-dimethylcyclohexylamine

N, N-dimethylformamide

n-butyl acetate

n-butyl methyl amine

n-butyl methyl ether

n-butylamine

n-butylbenzene

n-butylcyclohexane (n-butylciclohexane)

n-butyric acid

Nitrobenzene

Nitroethane

Nitromethane

N-methylacetamide

N-methylaniline

N-methylcyclohexylamine

N-methylformamide

N-methylimidazole

Nonane

Nonanoic acid

n-propyl acetate

n-propyl formate

n-propylbenzene

n-propylcyclohexane

Octane

Octanoic acid

Xylene (o-xylene)

Pentadecane (pentadecane)

Pentafluoropropionic acid

Pentane

Perfluorohexane

Perfluoropyridine

Petroleum ether

Piperidine

Propargyl alcohol (2-propynol)

Propionic acid

Propionitrile

Propiophenone

Propylene carbonate

p-xylene

Pyridine

Pyrrole

Pyrrolidine

Sulfolane

tert-butyl methyl ether

tert-butylbenzene

tert-butylcyclohexane

Tetrachloromethane

Tetrahydrofuran

Tetrahydropyran

Tetrahydrothiophene

Tetraline

Tetramethylguanidine

Tetramethylurea

Thioanisole

Toluene

Triacetin

Trichloroethene

Triethyl phosphate

Triethyl phosphite

Triethylamine

Trifluoroacetic acid

Trifluoro-m-cresol

Trifluoromethylbenzene

Trimethyl trimethyl orthoformate

Trimethyl trimethyl phosphate

Trimethyl trimethyl phosphite

 Trimethylacetic acid

 Tri-n-butylamine

 Tri-n-propylamine

Undecane

Valeric acid

Valeronitrile

Or mixtures thereof.

The following describes the charging process of the hybrid supercapacitor.

When a voltage is applied to the 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 being attracted to 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.

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. 7, the activated carbon is bonded to the anode current collector 10 made of aluminum and the cathode current collector 10 'made of copper with a binder, and then doped with iodine, which is a halogen element, to obtain polarity and conductivity. Electrodes 20 and 20 'having

In addition, a non-aqueous organic solvent propylene carbonate and chloronaphthalene, which is a halogen-substituted aromatic hydrocarbon, are mixed at a ratio of 1: 1, and 0.1-50 parts by weight of the ionic pore fullerene and 1-50 parts by weight of the ionic liquid polymer are contained in this mixture. A nonaqueous electrolyte solution is used.

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.

8A shows a discharge state. In the discharge state, as shown in the figure, lithium ion-containing fullerene 31 and anion 32 are randomly distributed.

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, charging by lithium ions contained in the lithium ion-encapsulated fullerene 31 is performed.

That is, in the present invention, after the primary charging is performed by the ionic liquid-polymer and the secondary charging by lithium ions contained in the lithium ion-containing fullerene 31 is completed, the present invention is present in the lithium-ion-containing fullerene 31. Tertiary charging is performed by degenerate molecular orbitals.

This will be described as follows.

first. When the power is applied, the first charge is first performed by the ionic liquid polymer, and the lithium ion containing fullerene (31) is moved to the negative electrode (20) by the electric field, so that the lithium ion contained in the lithium ion containing fullerene (31). Secondary charging is achieved by polarization. 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 are sequentially moved 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.

As described above, those skilled in the art to which the present invention pertains will understand that the present invention may be implemented in other specific forms without changing the technical spirit or essential features. Therefore, it should be understood that the embodiments described above are all illustrative and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention all changes or modifications derived from the meaning and scope of the claims to be described later rather than the detailed description and equivalent concepts thereof.

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: case

Claims (30)

As a supercapacitor having an electrode and an electrolyte,
The electrolyte comprises a fullerene containing ions, or a fullerene salt containing ions,
The charge is made by the ions contained in the fullerene,
Hybrid supercapacitor, characterized in that the charge by the fullerene itself. The 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 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 hybrid supercapacitor, wherein the hybrid supercapacitor is configured to have polarity with respect to fullerene, or configured 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. 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 Hybrid supercapacitor, characterized in that it has a polarity and conductivity 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. A hybrid supercapacitor characterized by the above. The hybrid supercapacitor according to claim 1, wherein the filling by the iontophorus fullerene is filled into the degenerate molecular orbital of the iontophorus fullerene. The hybrid supercapacitor of claim 1, wherein the fullerene is C60. The hybrid supercapacitor of claim 1, wherein the ions contained in the fullerene are metal ions. The hybrid supercapacitor of claim 10, wherein the ion contained in the fullerene is any one of lithium, sodium, potassium, cesium, magnesium, calcium, and strontium. The method of claim 10, wherein the ion corresponding to each of the fullerene encapsulated atoms are ^{Cl -, Br -, F -} , I -, ClO 3 -, ClO 4 -, BF 4 -, A1Cl4 -, PF 6 -, SbC 16 - Or SbF ₆ ^- any one or two or more thereof. As a super capacitor consisting of a current collector and an electrode,
An electrolyte composed of an ion-containing fullerene and an ionic liquid polymer filled between the positive electrode and the negative electrode constituting the electrode;
As the non-aqueous electrolyte containing the electrolyte is used,
The primary filling is made by the ionic liquid polymer,
Secondary charging by ions contained in fullerene,
Hybrid supercapacitor, characterized in that the third charge by the fullerene itself. The method of claim 13, wherein the non-aqueous electrolyte
(A) ion-containing fullerenes or salts thereof;
(B) an ionic liquid polymer;
(C) a non-aqueous organic solvent; And
(D) A hybrid supercapacitor comprising a halogen substituted aromatic hydrocarbon. The method of claim 13, wherein the non-aqueous electrolyte
(A) ion-containing fullerenes or salts thereof;
(C) a non-aqueous organic solvent; And
(D) A hybrid supercapacitor comprising a halogen substituted aromatic hydrocarbon. The method of claim 14,
The hybrid supercapacitor containing the said non-aqueous organic solvent and a halogen-substituted aromatic hydrocarbon in 1: 0.5-3, and adding 0.1-50 weight part of lithium ion inner fullerenes with respect to 100 weight part of this organic solvent mixture. The hybrid supercapacitor of claim 14, wherein a weight ratio of the non-aqueous organic solvent and the halogen-substituted aromatic hydrocarbon is 1: 1. 15. The hybrid supercapacitor of claim 14, wherein the halogen substituted aromatic hydrocarbon is selected from the group consisting of halogen substituted benzene, halogen substituted naphthalene and halogen substituted anthracene. 15. The method of claim 14 wherein the ionic liquid polymer is Cl and the cationic polymer of the formula (1) or the formula _{^{2 -, Br -, BF 4}} -, PF 6 -, (CF 3 SO 2) 2 N -, HPO 3 R 11- Wherein R ¹¹ is a C ₁ -C ₆ alkyl group and a hybrid supercapacitor comprising one or more anions selected from the group consisting of COOH ⁻ .
[Formula 1]

[Formula 2]

R in formulas 1 and 2 is a hydrogen atom, alkyl, cycloalkyl, allyl, aryl or alkylaryl, wherein alkyl is C ₁ -C ₆ , cycloalkyl is C ₃ -C ₁₀ , allyl is C ₂ -C _20, Aryl is C ₆ -C ₂₀ and n is an integer from 5,000 to 30,000. The method according to claim 14, wherein the ionic liquid polymer is an anionic polymer of formula 3 and R ₄ -P ⁺ (where R is a hydrogen atom, alkyl, cycloalkyl, allyl, aryl or alkylaryl, wherein alkyl is C _{1 -} C _6, cycloalkyl hybrid super capacitor C _3- C _10, allyl is C _2- C _20, aryl group include those which are combined with a C _6- C ₂₀ Im) anion.
[Formula 3]

N in the formula (3) is an integer of 5,000 to 500,000. 15. The hybrid supercapacitor of claim 14, wherein the ionic liquid polymer is a dual polymer of Formula 4.
[Formula 4]

In formula 4 A ^- is a SO ₃ ^- or PO ₃ H ^- or CO ₂ ^-, n is an integer of from 5,000 to 300,000. The method of claim 13, wherein the non-aqueous electrolyte,
The non-aqueous organic solvent and the halogen-substituted aromatic hydrocarbon are mixed at 1: 0.5 to 3, and 0.1-50 parts by weight of the electrolyte lithium ionpofullerene, a cationic polymer or an anionic polymer or a double polymer with respect to 100 parts by weight of the organic solvent mixture. A hybrid supercapacitor further comprising 1 to 50 parts by weight of the ionic liquid polymer. The hybrid supercapacitor of claim 18, wherein the halogen-substituted benzene is represented by Chemical Formula 5. 19.
[Formula 5]

In formula 1 R ¹ to R ⁶ each independently are a C ₁ ~ C ₆ alkyl group, a halogen or a C ₁ ~ C ₆ substituted with a halogen atom alkilgiyi unsubstituted, are necessarily substituted with one or more halogen. 19. The hybrid supercapacitor of claim 18, wherein the halogen substituted naphthalene is represented by Formula 6.
[Formula 6]

In Formula 2 R ¹ to R ⁸ each independently are a C ₁ ~ C ₆ alkyl group, a halogen or a C ₁ ~ C ₆ substituted with a halogen atom alkilgiyi unsubstituted, are necessarily substituted with one or more halogen. The hybrid supercapacitor of claim 18, wherein the halogen-substituted anthracene is represented by Formula 7.
[Formula 7]

In Formula 3 R ¹ to R ¹⁰ are each independently selected from unsubstituted C ₁ ~ C ₆ alkyl group, a halogen or a halogen atom being substituted with C ₁ ~ C ₆ alkilgiyi, and be substituted one or more halogen. The hybrid supercapacitor of claim 13, wherein the non-aqueous organic solvent is a cyclic carbonate, a chain carbonate, or any one or a mixture of cyclic carbonates and chain carbonates. 27. The method of claim 26, wherein the cyclic carbonate is at least one carbonate selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, γ-butyrolactone and mixtures thereof, wherein the chain carbonate is Dimethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, n-butyl methyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl propyl carbonate, ethyl isopropyl carbonate, dipropyl carbonate, fluoro dimethyl carbonate, difluoro dimethyl carbonate, Trifluorodimethyl carbonate, tetrafluorodimethyl carbonate, fluorodimethyl carbonate, fluoroethyl methyl carbonate, difluoroethyl methyl carbonate, trifluoroethyl methyl carbonate, methyl acetate, ethyl acetate, propionate Methyl fluoroacetate, methyl difluoroacetic acid, methyl trifluoroacetic acid, ethyl fluoroacetate, ethyl difluoroacetic acid, ethyl trifluoroacetic acid, methyl fluoropropionate, methyl difluoropropionate, trifluoropropionic acid A hybrid supercapacitor comprising at least one carbonate selected from the group consisting of methyl and mixtures thereof. The hybrid supercapacitor of claim 1, wherein the charging potential of the ion-containing fullerene is greater than or equal to a reduction potential. 15. The supercapacitor according to claim 14, wherein said ion-containing fullerene is intercalated with a halogen substituted aromatic hydrocarbon. 28. The supercapacitor of claim 27, comprising improving charging duration by preventing natural discharge by said intercalation.

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