KR20190110947A - battery - Google Patents

Abstract

According to the present invention, a biopotential charging micro battery is a thin film battery including electrodes and an electrolyte. One of the electrodes is made of a carbon nanotube. A fullerene containing ions or an electrolyte including a fullerene salt containing ions is included in the carbon nanotube. Charging is carried out by the ions contained in the fullerene by electrodes attached to a body to detect a potential generated by the body and the potential detected by the electrodes. The ion-containing fullerene, which is an electrolyte, is included in the carbon nanotube to be used. Therefore, the present invention can be charged by a minute potential to be charged by an electromyogram, an electrocardiogram, a brainwave, or a biopotential generated in a specific organ. Also, the nano-sized fullerene is used as an electrolyte to markedly increase energy storage density to reduce size and weight and improve charging characteristics and discharging characteristics. Also, the physically and chemically stable fullerene is used to store energy in a physically and chemically stable manner.

Description

Biopotential charging microbattery {battery}

The present invention relates to a biopotential charging microbattery capable of charging at a very fine voltage.

More specifically, after the carbon nanotubes are grown to have a polarity in the current collector, fullerenes containing ions (hereinafter referred to as "ion-containing fullerenes") are injected into the carbon nanotubes and used as an electrolyte. It's a new concept of microbattery that allows charging at very small voltages.

The present invention is characterized by the ability to charge a very low voltage, such as biopotential by dramatically lowering the charging voltage, significantly improve the charging capacity, improve the charging characteristics and discharge characteristics, physical and chemical advantages There is this. In addition, the use of fullerene, a nano-sized molecule, has the advantage of increasing energy density, miniaturization, and weight reduction.

The present invention is characterized in that the thin film is attached to the human body or inserted into a specific part, and charges an electric potential generated in the human body to operate an external device.

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 prior art as described above has a problem that can not be stored at a small voltage to store the bioenergy generated in the human body.

An object of the present invention is to solve the above-mentioned conventional problems, in particular, by making any one of the electrodes of carbon nanotubes, fullerenes containing ions or fullerene salts containing ions inside the carbon nanotubes The battery is formed by injecting an electrolyte containing it, so that charging is possible at a very small potential.

In other words, EMG, electrocardiogram, electroencephalogram, or any other living body electric charges generated in a living body can be charged.

The present invention is attached to the human body (or living body), or inserted into the procedure to be able to use the bioenergy generated in the human body.

The "biopotentially charged microbattery" of the present invention is a thin film microbattery having an electrode and an electrolyte, wherein one of the electrodes is made of carbon nanotubes, and fullerenes or ions containing ions are contained in the carbon nanotubes. Charged by the ion contained in the fullerene is made by enclosing an electrolyte containing an impregnated fullerene salt, and an electricoid attached to a living body to detect a potential occurring in the living body and a potential detected through the electroroid. Characterized in that the biopotential charging micro-battery, characterized in that made.

The carbon nanotube electrode is configured to have polarity with respect to the fullerene containing ions, and the other one is configured to have polarization with respect to the fullerene containing ions.

In one aspect of the present invention, the electrode of any one of the cathode or the anode is made of carbon nanotubes, injecting an electrolyte containing a fullerene containing ions, or a fullerene salt containing ions in the carbon nanotubes, 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 particular, the "biopotentially charged microbattery" of the present invention is constructed so that carbon nanotubes are polarized with respect to ion-containing fullerenes and used as one electrode of a battery, and then charged with ion-free fullerenes in the carbon nanotubes as an electrolyte. Thereby, there is an effect that the filling by the ions contained in the ion-encapsulated fullerene is made.

In addition, since the ion nano-fullerene which is an electrolyte is contained in the carbon nanotube, it is possible to charge at an extremely fine voltage such as a biopotential.

In addition, by using fullerene, a nano-sized molecule, as an electrolyte, the energy storage density is significantly increased, thereby making it possible to manufacture thin films, small sizes, 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 the present invention biopotential charging microbattery,
Figure 1b is a schematic diagram showing the state of charge of the present invention biopotential charging micro battery,
Figure 1c is a schematic diagram showing an enlarged state of charge of the present invention biopotential charging microbattery,
1D is a schematic view showing the configuration of the present invention biopotential charging microbattery,
1E is a use state diagram showing a use state of the present invention biopotential charging microbattery,
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;
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 waveform diagram showing an example of a myoelectric signal;

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.

The biopotential charging microbattery according to the present invention, as shown in Fig. 1d, constitutes an electrode in which carbon nanotubes 35 are grown on a current collector 10 on one side of the microbattery. Ion-containing fullerenes are injected into the carbon nanotubes 35, and a non-aqueous electrolyte containing the ion-containing fullerenes is used.

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 constitute an anode current collector in aluminum, and the second current collector 10 ′ may constitute a cathode current collector in copper.

The carbon nanotubes 35 of the first electrode 20 formed on the first current collector 10 are configured to have polarity with respect to the ion-containing fullerene, and the second electrode bonded to the second current collector is also ion-containing fullerene. It is configured to have only polarity for.

In another embodiment, the first electrode of the carbon nanotubes may be provided in each of the first current collector and the second current collector.

The second electrode having polarity with respect to the 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.

The second electrode having polarity with respect to ion-containing fullerene may be formed of any one of activated carbon, graphene, carbon nanotubes, or fullerene in the current collector.

Porous activated carbon, for example, 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.

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, when the two-dimensional plane of graphene is bonded to the current collector surface in parallel to each other, an electrode having polarization with respect to ion-containing fullerene is produced.

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 the carbon nanotubes are grown on the current collector, the chirality is controlled to grow so that there is no 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 micro-battery of the present invention is filled between the current collector, the first electrode of carbon nanotubes provided by the growth or bonding method on the current collector, the second electrode made of activated carbon, and the like, and then the first and second electrodes. Non-aqueous electrolyte solution.

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, the battery can be made using the ion-containing fullerene, as well as the battery can be made using the ion-containing 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.

(If the above is true, please describe the reaction of the ionic liquid polymer in detail.)

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, and 300 parts by weight based on 100 parts by weight of the ion-containing fullerene. If it exceeds, there is a problem that difficult to control the concentration, if less than 50 parts by weight may not be made smoothly filling reaction.

(It was written by myself. Please correct it.)

(Weights are expressed in parts by weight, parts in parts by weight. On the other hand, parts by weight can be expressed in percent by weight, which means that the minimum must be set to 100 to reduce the rights.)

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.

In the present invention, the weight ratio of the non-aqueous organic solvent and the halogen-substituted aromatic hydrocarbon may be 1: 0.1 to 3, preferably 1: 0.8 to 1.5, and most preferably 1: 1. If the weight ratio is less than 1: 0.1, there is a problem that it is difficult to adjust the internal resistance, and if it exceeds 1: 3, there is a problem that it is difficult to adjust the concentration.

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 biopotential charging microbattery according to the present invention.

On the other hand, when voltage is applied to the biopotentially charged microbattery of the present invention, the first charge is first performed in an ionic liquid polymer which has almost no movement, and the positive electrode 20 is provided through the negative electrode 20 and the carbon nanotube 35. An electric field is formed between '), and the iontophorus fullerene 31 is moved toward the carbon nanotube 35 by the electric field, and the anion 32 is moved toward the positive electrode 20' to perform secondary charging.

That is, the filling by the ions contained in the ion-containing fullerene 31 is performed. Reference numeral 33 indicates a metal atom ion contained in the ion.

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 carbon nanotubes are formed on the negative electrode current collector 10. The negative electrode 20 is made by growing 35.

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 technical spirit of the present invention can be easily understood from the present embodiment.

First, as shown in FIG. 1D, carbon nanotubes are grown on a negative electrode current collector 10 made of aluminum, and activated carbon is bonded to a positive electrode current collector 10 'made of copper.

The battery is made by injecting lithium ion containing fullerene into the carbon nanotubes and then sealing the case.

In another embodiment of the present invention, a non-aqueous electrolyte solution containing the ion-containing fullerene is filled between the electrodes.

First, the non-aqueous electrolyte is a 1: 1 mixture of a non-aqueous organic solvent and a halogen-substituted aromatic hydrocarbon, and 0.1 to 50 parts by weight of the electrolyte lithium ion-inpofullerene is included with respect to 100 parts by weight of the mixture.

Naturally, the lithium ion-containing fullerene is injected into carbon nanotubes.

In another embodiment, the present invention is a 1: 1 mixture of the non-aqueous organic solvent and the halogen-substituted aromatic hydrocarbon, 0.1 to 50 parts by weight of the lithium ion-inpofullerene, cationic polymer or anionic polymer or dual polymer with respect to 100 parts by weight of the mixture It fills the non-aqueous electrolyte solution which 1-50 weight part of any one of polymers further contains.

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

The thin film battery according to the present embodiment is used by being attached to a living body, as shown in Fig. 1E.

The bioelectricity is then collected through the electroids 51, 52, and the biopotential is stored in the battery of the present invention.

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 the biopotential charging, the first charge is first performed in the inactive ionic liquid polymer.

Next, an electric field is formed between the carbon nanotube 35, which is a part of the negative electrode 10, and the positive electrode 10 ', and the positively charged fullerene 31 containing lithium ions is moved toward the carbon nanotube 35 by the electric field. Thereby contacting the carbon nanotubes 35. At this time, secondary charging by lithium ions contained in the lithium ion-encapsulated fullerene 31 is performed.

At this time, since the carbon nanotubes 35 used as the negative electrode and the lithium ion-containing fullerene 31 are very close to each other, charging at an extremely fine voltage is possible.

For example, in the case of EMG, a voltage of several microvolts to hundreds of microvolts is generated depending on the momentum or the degree of force applied. The battery of the present invention is a carbon nanotube 35 used as a negative electrode and an electrolyte. Since the distance between the lithium ion-containing fullerenes 31 is close, charging at such a minute voltage is possible.

This will be described as follows.

first. The lithium ion-encapsulated fullerene 31 is moved to the carbon nanotube 35 which is a part of the negative electrode 20 by moving the user's muscles, and is charged by the polarization phenomenon of lithium ions contained in the lithium-ion-containing fullerene 31. This is done. At this time, the polarization of the carbon nanotubes 35 is used.

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.

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: electron 35: carbon nanotube
40: Case 51, 52: Electroroid
60: EMG waveform

Claims (28)

A battery consisting of a thin film having an electrode and an electrolyte,
One of the electrodes is made of carbon nanotubes,
The carbon nanotubes are made by embedding an electrolyte including a fullerene containing ions or a fullerene salt containing ions,
An electroid attached to a living body and detecting a potential generated in the living body;
By the potential detected through the electroid,
The biopotential charging micro battery, characterized in that the charge by the ions contained in the fullerene is made. The biopotential charging micro-battery of claim 1, wherein the first electrode of the carbon nanotubes into which the ion-encapsulated fullerene is injected is polarized with respect to the fullerene containing the ions. The biopotential charging micro-battery of claim 1, wherein the second electrode corresponding to the carbon nanotube electrode into which the ion-encapsulated fullerene is injected is configured to have polarity with respect to the fullerene containing the ion. The biopotential charging micro-battery according to claim 3, wherein the second electrode having polarity with respect to the ion-containing fullerene is composed of activated carbon or Teflon. The method of claim 3, wherein the second electrode having polarity with respect to the ion-containing fullerene is configured to have a polarity with respect to the ion-containing fullerene by controlling the bonding direction of the graphene, or by controlling the chirality of the carbon nanotubes A biopotential charging micro-battery, characterized in that it is configured to have polarity with respect to the ion-containing fullerene, or configured to have polarity with respect to the ion-containing fullerene by controlling the bonding direction of the fullerene. The biopotential charging micro-battery of claim 1, wherein the electrode is formed on one side or each of the carbon nanotubes. The biopotential charging micro-battery of claim 1, wherein the fullerene is C60. The biopotential charging micro battery according to claim 1, wherein the ions contained in the fullerene are metal ions. The biopotential charging micro battery according to claim 8, wherein the ion contained in the fullerene is any one of lithium, sodium, potassium, cesium, magnesium, calcium, and strontium. The method of claim 8 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 ^- in any biological potential charged micro-battery, wherein one or two or more kinds. A micro battery comprising a current collector and an electrode bonded or formed on the current collector,
One of the electrodes is made of carbon nanotubes,
Fullerenes or salts containing ions are injected into the carbon nanotubes,
The biopotential charging micro-battery further comprises a non-aqueous electrolyte containing the ion-containing fullerene or a salt thereof. The method of claim 11, 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 biopotential charged microbattery comprising a halogen substituted aromatic hydrocarbon. The method of claim 11, wherein the non-aqueous electrolyte
(A) ion-containing fullerenes or salts thereof;
(C) a non-aqueous organic solvent; And
(D) A biopotential charged microbattery comprising a halogen substituted aromatic hydrocarbon. The method of claim 12,
A non-aqueous organic solvent and a halogen-substituted aromatic hydrocarbon are mixed at a ratio of 1: 0.5 to 3, and a biopotential-charged micro-battery comprising 0.1 to 50 parts by weight of lithium ion inner fullerene is added to 100 parts by weight of the organic solvent mixture. The biopotential charging micro-battery of claim 12, wherein the weight ratio of the non-aqueous organic solvent and the halogen-substituted aromatic hydrocarbon is 1: 1. 13. The biopotential charged microbattery of claim 12, wherein the halogen substituted aromatic hydrocarbon is selected from the group consisting of halogen substituted benzene, halogen substituted naphthalene and halogen substituted anthracene. The method of claim 12, 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 COOH ^- at least one anion selected from the group consisting of a biopotential charged micro-battery comprising.
[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 of claim 12, 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 is C _3- C _10, allyl is C _2- C _20, aryl is a bio potential charged micro-battery, including that it is combined with ₂₀ Im) anion C _6- C.
[Formula 3]

N in the formula (3) is an integer of 5,000 to 500,000. The biopotential charging micro-battery of claim 12, 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 12, 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 biopotential charged micro battery further comprising 1 to 50 parts by weight of an ionic liquid polymer. The biopotential charging micro-battery of claim 16, wherein the halogen-substituted benzene is represented by Chemical Formula 5.
[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 biopotential charging micro-battery of claim 16, wherein the halogen-substituted naphthalene is represented by Chemical 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 biopotential charging micro-battery of claim 16, 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 biopotential charging micro-battery of claim 12, 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. 25. The method of claim 24, 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 biopotential charged micro-battery comprising at least one carbonate selected from the group consisting of methyl and mixtures thereof. 26. The biopotential charging microbattery of claim 1 or 25, wherein the charging by iontofullerene itself is charged to the degenerate molecular orbital of the iontofullerene. 30. The biopotential charging microbattery of claim 29, wherein the number of electrons charged in the degenerate molecular orbital of the iontophorus fullerene is 5 or less. 12. The biopotential charging microbattery of claim 1 or 11, wherein the charging potential is greater than or equal to the reduction potential of the iontofullerene.

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