KR101815902B1 - Manufacturing method of electrode active material for ultracapacitor and manufacturing method of ultracapacitor electrode using the electrode active material - Google Patents

Manufacturing method of electrode active material for ultracapacitor and manufacturing method of ultracapacitor electrode using the electrode active material Download PDF

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KR101815902B1
KR101815902B1 KR1020160051206A KR20160051206A KR101815902B1 KR 101815902 B1 KR101815902 B1 KR 101815902B1 KR 1020160051206 A KR1020160051206 A KR 1020160051206A KR 20160051206 A KR20160051206 A KR 20160051206A KR 101815902 B1 KR101815902 B1 KR 101815902B1
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activated carbon
electrode
graphene oxide
ultracapacitor
graphene
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KR20170122370A (en
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노광철
강원섭
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한국세라믹기술원
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The present invention relates to a method for producing a graphite oxide, comprising the steps of: forming a graphite oxide; introducing the graphite oxide into a polar solvent; peeling the graphite oxide by ultrasonic treatment to form a graphene oxide dispersion; A step of adding an activated carbon to a graphene oxide mixed dispersion to form an activated carbon-graphen oxide mixed dispersion; and a step of adding an isocyanate-based compound to the activated carbon-graphene oxide mixed dispersion to prepare an isocyanate- Introducing an isocyanate-introduced activated carbon-graphene oxide complex into a polar solvent; introducing an organic compound containing an amino group and a pyrimidine group into the activated carbon-graphene oxide complex; Activated carbon - graphene Side composite; and a step of reducing heat treatment of the activated carbon-graphen oxide complex into which the nitrogen functional group is introduced to obtain a nitrogen-doped activated carbon-graphene composite, and a method for producing the electrode active material for an ultracapacitor, And more particularly, to a method of manufacturing an ultracapacitor electrode using an electrode active material.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing an electrode active material for an ultracapacitor, and a method of manufacturing an electrode material for an ultracapacitor using the electrode active material for the ultracapacitor.

The present invention relates to a method for producing an electrode active material for an ultracapacitor and a method for producing an ultra capacitor electrode using the electrode active material for the ultracapacitor. More particularly, the present invention relates to a method for producing an electrode active material for an ultra- A method for producing an electrode active material for an ultracapacitor capable of preventing deterioration of electrochemical performance and improving electric conductivity and being capable of realizing a high non-storage capacity by substituting an oxygen functional group on the surface with a nitrogen functional group, And more particularly, to a method of manufacturing an ultracapacitor electrode using an electrode active material.

In general, an ultracapacitor is also referred to as an electric double layer capacitor (EDLC) or a supercapacitor, which is formed by a pair of electrodes and a conductor, each having a different sign at the interface between the electrode and the conductor, (Electric double layer) of the charge / discharge operation is used, and the deterioration due to the repetition of the charging / discharging operation is very small, so that the device is not required to be repaired. Accordingly, ultracapacitors are mainly used for IC (integrated circuit) backup of various electric and electronic devices. Recently, they have been widely used for toys, solar energy storage, HEV (hybrid electric vehicle) have.

Such an ultracapacitor generally comprises two electrodes of a positive electrode and a negative electrode impregnated with an electrolytic solution, a separator of a porous material interposed between the two electrodes to allow only ion conduction and to prevent a short circuit, A gasket for preventing short-circuiting, and a case for packaging them.

The performance of the ultracapacitor having such a structure is determined by the electrode active material, the electrolyte, etc. In particular, the major performance such as the capacitance is largely determined by the electrode active material.

Activated carbon is an ultracapacitor active material that exhibits a non-storage capacity by physical adsorption and desorption of ions due to its high specific surface area. A conductive material such as carbon black is used in order to improve the electrical conductivity and the physical properties of the electrode when the electrode is made into an electrode using activated carbon. However, it is difficult to disperse the conductive material and the conductive material does not surround the entire surface of the activated carbon particles, Resulting in a decrease in capacity per volume as the electrode density decreases.

Also, the activated carbon produced by the alkali activation and the steam activation method has a certain amount of oxygen functional groups on the surface thereof, which causes a side reaction with the electrolyte during charging and discharging, resulting in a decrease in the electrochemical performance.

Korean Patent Publication No. 10-1079317

The problem to be solved by the present invention is to provide a method for manufacturing a carbon nanotube which is capable of preventing the deterioration of electrochemical performance and preventing the deterioration of electrochemical performance by substituting nitrogen functional groups on the surface with graphene having high specific surface area and excellent electrical conductivity while being coated on the surface of activated carbon And a method of manufacturing an electrode active material for an ultracapacitor which can realize a high non-storage capacity.

Another object to be solved by the present invention is to provide an electrode which does not require the use of a conductive material and has a high specific surface area and is easy to express in capacity, The present invention provides a method of manufacturing an ultracapacitor electrode which can improve the specific stock amount and utilize inherent physical properties such as excellent conductivity and high specific surface area possessed by graphene.

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The present invention relates to a method for producing a graphite oxide, comprising the steps of: forming a graphite oxide; introducing the graphite oxide into a polar solvent; peeling the graphite oxide by ultrasonic treatment to form a graphene oxide dispersion; A step of adding an activated carbon to a graphene oxide mixed dispersion to form an activated carbon-graphen oxide mixed dispersion; and a step of adding an isocyanate-based compound to the activated carbon-graphene oxide mixed dispersion to prepare an isocyanate- Introducing an isocyanate-introduced activated carbon-graphene oxide complex into a polar solvent; introducing an organic compound containing an amino group and a pyrimidine group into the activated carbon-graphene oxide complex; Activated carbon - graphene Comprising: side presented complex is formed and is introduced into the activated carbon of the nitrogen-functional group-yes-reduction by heating the pin oxide complex nitrogen-doped activated carbon - Yes it provides a process for the production of ultra-capacitors for the electrode active material comprising the steps of obtaining a composite pin.

The step of forming the graphite oxide includes mixing graphite, H 2 SO 4 , K 2 S 2 O 8 and P 2 O 5 with stirring, cooling the resultant to room temperature, adding and leaving distilled water, in that by selectively separating the precipitate from the left output stage and, optionally, a dispersing precipitate came up with separation of distilled water and, an adding step of adding a H 2 SO 4 and KMnO 4 and H 2 SO 4 and KMnO 4 results Adding H 2 O 2 to the solution to which distilled water has been additionally added to cause the color of the solution to change to bright yellow while bubbling occurs, and selectively separating the precipitate from the solution changed to bright yellow.

The isocyanate compound may include at least one material selected from isocyanate, diisocyanate and triisocyanate.

The organic compound containing an amino group and a pyrimidine group may be 2-amino-4-hydroxy-6-methylpyrimidine, 2-amino-4,6-dimethylpyrimidine Amino-4-methylpyrimidine, 2-amino-4,6-dimethylpyrimidine and 2-amino-4-methylpyrimidine.

The activated carbon-graphene oxide mixed dispersion preferably contains 1 to 30 parts by weight of graphene oxide per 100 parts by weight of the oxidized activated carbon.

The reduction heat treatment is preferably performed at a temperature of 450 to 900 캜 in a nitrogen gas atmosphere.

The present invention also relates to a method for producing an electrode, comprising the steps of: forming an electrode active material for an ultracapacitor and a binder in a dispersion medium to form a composition for electrode in a kneaded state; forming the electrode composition in the form of an ultracapacitor electrode; And drying the molded product to form an ultracapacitor electrode.

It is preferable that the binder is mixed in an amount of 1 to 20 parts by weight based on 100 parts by weight of the electrode active material for the ultracapacitor.

The forming step may include rolling the electrode composition using a roll press molding machine to form a sheet type electrode. The pressure applied to the electrode composition by the roll press molding machine is 1 To 20 ton / cm 2, the heating temperature applied to the electrode composition is in the range of 40 to 150 ° C, and the sheet type electrode preferably has an average thickness of 100 to 300 μm.

The drying is preferably performed in a vacuum atmosphere at a temperature of 120 to 350 캜.

The present invention also provides a method of manufacturing a thin film capacitor, comprising: a positive electrode including an ultracapacitor electrode manufactured by the above manufacturing method; a negative electrode including an ultracapacitor electrode manufactured by the manufacturing method; and a negative electrode disposed between the positive electrode and the negative electrode, And a gasket for sealing the case, wherein the cathode, the separator, and the cathode are disposed inside the case and the electrolyte is injected into the case.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a first separator for preventing a short circuit, an anode including the ultracapacitor electrode manufactured by the manufacturing method, a second separator for preventing short- A negative electrode including the prepared ultracapacitor electrode is wound in the form of a roll in the form of a coiled roll, a first lead wire connected to the negative electrode, a second lead wire connected to the positive electrode, And a seal rubber for sealing the case, wherein the roll revolver is impregnated with an electrolytic solution.

According to the present invention, since graphene having a high specific surface area and excellent electrical conductivity is coated on the surface of an activated carbon, the oxygen functional group on the surface is replaced by a nitrogen functional group, thereby preventing deterioration of electrochemical performance and improving electric conductivity An electrode active material for an ultracapacitor capable of realizing a high non-storage capacity can be produced.

Although the conductive material such as carbon black is used for improving the electrical conductivity and the physical properties of the electrode when the electrode is made into an electrode using activated carbon, it is difficult to disperse the whole surface of the activated carbon particle because the conductive material does not surround the conductive material. (Such as Super-P) is not required in the production of the ultracapacitor electrode of the present invention, the specific surface area is high, the electric conductivity is excellent, and the capacity expression The electrode can be manufactured as an electrode containing easy graphene. Therefore, the conductivity can be improved, the density can be increased by increasing the density of the electrode, and the electrode having improved storage capacity can be manufactured compared to the conventional electrode.

The ultracapacitor of the present invention uses an electrode containing graphene having a high specific surface area, excellent electric conductivity and easy to develop capacity, and can improve the conductivity and the specific stock amount, and the excellent conductivity and high ratio It is possible to utilize inherent physical properties such as surface area.

1 is a view showing an oxidized activated carbon.
2 is a view showing a state where an isocyanate group is formed by reacting with an oxygen functional group on the surface of the activated carbon 100. FIG.
3 is a view showing a nitrogen doped activated carbon-graphene composite.
4 is a sectional view of a coin type ultracapacitor cell to which an ultracapacitor electrode is applied, according to an embodiment of the present invention.
5 to 8 are views showing an ultracapacitor cell according to another example.
9 is a scanning electron microscope (SEM) photograph showing the shape of the nitrogen-doped activated carbon-graphene composite prepared according to the experimental example.
10 is an N1s XPS (X-ray Photoelectron Spectroscopy) analysis graph of the nitrogen-doped activated carbon-graphene composite prepared according to Experimental Example.
11 is a graph showing discharge curves of an ultracapacitor manufactured according to Experimental Examples and Comparative Examples.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not. Wherein like reference numerals refer to like elements throughout.

The conductive material (for example, carbon black) to be added in the production of the activated carbon electrode is a material having little non-storage capacity during charging and discharging, and it is recommended to use the minimum amount for realizing the physical properties of the electrode and improving the electric conductivity. In addition, a side reaction during the electrochemical reaction by the oxygen functional group remaining on the surface of the activated carbon may show a decrease in the electrochemical performance. Activated carbon produced by alkali activation and steam activation method has a certain amount of oxygen functional group on the surface thereof, which causes a side reaction with an electrolyte during charging and discharging, resulting in a decrease in electrochemical performance.

In the present invention, a method of introducing a nitrogen functional group onto the surface of the activated carbon while graphen having a high specific surface area and an excellent electrical conductivity is coated on the surface of the activated carbon is proposed. It is possible to produce a nitrogen-doped activated carbon-graphene composite having a high electric conductivity and to manufacture a high-density ultracapacitor electrode which does not require a conductive material. In the production of the ultracapacitor electrode, a conductive material such as carbon black is not required. The surface of the activated carbon is coated with graphene, thereby improving the electrical conductivity. The oxygen functional group on the activated carbon surface is replaced with the nitrogen functional group, .

Since the conductive material (for example, Super-P) is not required in the production of the ultracapacitor electrode of the present invention, and the graphene having high specific surface area, excellent electric conductivity, It is possible to produce an electrode having an increased specific volume compared to conventional electrodes.

The method for producing an electrode active material for an ultracapacitor according to a preferred embodiment of the present invention includes the steps of forming a graphite oxide, introducing the graphite oxide into a polar solvent, peeling the graphite oxide by ultrasonic treatment to form a graphene oxide dispersion A step of oxidizing the activated carbon in an acidic solution containing an oxygen component, introducing the oxidized activated carbon into the graphene oxide dispersion to form a mixed dispersion of activated carbon and graphene oxide, Graphen oxide complex into which an isocyanate has been introduced; and a step of dispersing the activated carbon-graphene oxide complex into which the isocyanate has been introduced in a polar solvent to prepare an activated carbon- Midigan To form an activated carbon-graphen oxide composite into which a nitrogen functional group is introduced, and a step of reducing heat treatment of the activated carbon-graphen oxide composite into which the nitrogen functional group is introduced to obtain a nitrogen-doped activated carbon-graphene composite .

The step of forming the graphite oxide includes mixing graphite, H 2 SO 4 , K 2 S 2 O 8 and P 2 O 5 with stirring, cooling the resultant to room temperature, adding and leaving distilled water, in that by selectively separating the precipitate from the left output stage and, optionally, a dispersing precipitate came up with separation of distilled water and, an adding step of adding a H 2 SO 4 and KMnO 4 and H 2 SO 4 and KMnO 4 results Adding H 2 O 2 to the solution to which distilled water has been additionally added to cause the color of the solution to change to bright yellow while bubbling occurs, and selectively separating the precipitate from the solution changed to bright yellow.

The isocyanate compound may include at least one material selected from isocyanate, diisocyanate and triisocyanate.

The organic compound containing an amino group and a pyrimidine group may be 2-amino-4-hydroxy-6-methylpyrimidine, 2-amino-4,6-dimethylpyrimidine Amino-4-methylpyrimidine, 2-amino-4,6-dimethylpyrimidine and 2-amino-4-methylpyrimidine.

The activated carbon-graphene oxide mixed dispersion preferably contains 1 to 30 parts by weight of graphene oxide per 100 parts by weight of the oxidized activated carbon.

The reduction heat treatment is preferably performed at a temperature of 450 to 900 캜 in a nitrogen gas atmosphere.

The ultracapacitor electrode according to a preferred embodiment of the present invention includes a step of forming a composition for electrode in a paste state by mixing an electrode active material for an ultracapacitor and a binder in a dispersion medium and forming the electrode composition in the form of an ultracapacitor electrode And drying the molded product in the electrode form to form an ultracapacitor electrode.

It is preferable that the binder is mixed in an amount of 1 to 20 parts by weight based on 100 parts by weight of the electrode active material for the ultracapacitor.

The forming step may include rolling the electrode composition using a roll press molding machine to form a sheet type electrode. The pressure applied to the electrode composition by the roll press molding machine is 1 To 20 ton / cm 2, the heating temperature applied to the electrode composition is in the range of 40 to 150 ° C, and the sheet type electrode preferably has an average thickness of 100 to 300 μm.

The drying is preferably performed in a vacuum atmosphere at a temperature of 120 to 350 캜.

An ultracapacitor according to a preferred embodiment of the present invention includes an anode including the ultracapacitor electrode manufactured by the manufacturing method, a cathode including the ultracapacitor electrode manufactured by the manufacturing method, and a cathode disposed between the anode and the cathode A separator for preventing the anode and the cathode from short-circuiting, a case in which the anode, the separator, and the cathode are disposed and into which an electrolyte is injected, and a gasket for sealing the case.

An ultracapacitor according to a preferred embodiment of the present invention includes a first separator for preventing a short circuit, an anode including an ultracapacitor electrode manufactured by the manufacturing method, and a second separator for preventing short- And a negative electrode including an ultracapacitor electrode manufactured by the above manufacturing method are sequentially stacked and coiled to form a roll, a first lead wire connected to the negative electrode, a second lead wire connected to the positive electrode, A case for accommodating the roll revolver, and a sealing rubber for sealing the case, wherein the roll revolver is impregnated with the electrolytic solution.

Hereinafter, a method of manufacturing an electrode active material for an ultracapacitor, a method of manufacturing an ultracapacitor electrode using the electrode active material for the ultracapacitor, and an ultracapacitor using the ultracapacitor electrode will be described in more detail.

The carbon material is generally classified into three-dimensional diamond and graphite, two-dimensional graphene, one-dimensional carbon nanotube, and zero-dimensional buckyball depending on its structure. Graphene is a term made by combining graphite, which means graphite, and suffix -ene, which means a molecule having a double bond of carbon. Three out of four outermost electrons constituting graphene form a sp 2 hybrid orbital, forming a strong covalent σ bond, while the remaining one electron forms a π bond with other carbons around it, Shape 2-dimensional structure. The single-layer graphene has a thickness of about 0.34 nm and is very thin and has excellent mechanical strength, thermal and electrical properties, flexibility and transparency.

Grapin became widely known as Novoselov and Professor Geim of the University of Manchester announced the world's first method of separating graphene from pencil lead graphite using the adhesion of Scotch tape. First, prepare graphite flakes, conventional scotch tape, and SiO 2 wafers. The prepared flakes are put on a scotch tape and folded several times and repeated. After this process is completed, the tape is placed on a SiO 2 wafer, rubbed off the remaining flake marks, and the tape is removed to obtain a multi-layered graphene from one layer of graphene.

The reason why this method is possible is to look at the atomic structure of graphene. Graphene has three carbon atoms forming a strong covalent bond on a two-dimensional plane, while a relatively weak van der Waals force in the vertical direction, resulting in very low coefficient of friction between layers, resulting in weak adhesion of the scotch tape It becomes possible to separate it. The exfoliated graphene was very simple to prepare for the sample, and exhibited excellent electrical and structural properties, which played a role in rapidly spreading the basic research of graphene. However, since the area is only a micrometer level and the yield is low, there is a limit to the manufacturing method for various applications.

The fracture stress of graphene is ~ 40 N / m, the theoretical limit value is about 125 GPa, and the modulus of elasticity is about ~ 1.0 TPa which is more than 200 times of steel. This is because there is a hard carbon bond and there is no bond in the fault. In addition, it can be increased by 20% in a plane axis direction, which is much larger than any other crystal. Also, as temperature rises, graphene continues to shrink by two-dimensional phonons, and at the same time has a very flexible and well-cracked character when pulled strongly.

Graphene has a thermal conductivity of about 5,000 W / m · K at room temperature, which is superior to carbon nanotubes or diamond. It is 50% higher than carbon nanotubes and 10 times larger than metals such as copper and aluminum. This is because graphene can easily transmit atomic vibrations. This excellent thermal conductivity also affects the long average free path of electrons. On the other hand, graphite with graphene laminate has a disadvantage in that the thermal conductivity (about 100 times) is significantly lowered in the vertical direction.

The maximum electron mobility of graphene at room temperature is about 200,000 cm 2 / Vs. This is known to be due to the very small degree of scattering of electrons in the case of graphene, which leads to a long average free path. Therefore, resistance is lower than 35% of copper with very low resistance. Also, in the case of graphene, it does not lose its electrical conductivity even when the area is increased or decreased by more than 10%.

Generally, top-down graphene production methods using graphite can be classified into three types of mechanical peeling, chemical peeling, and non-oxidative peeling.

Mechanical exfoliation refers to the removal of mechanical forces from graphite crystals consisting of van der Waals weak bonds. As if a thin film peeled off smoothly from a pencil lead and the writing was written, it was made from graphene using graphite crystals. This method is possible because electrons of the π-orbital of graphene spread widely on the surface and have a smooth surface.

The chemical stripping method is a method based on a solvent that uses an oxidation and reduction reaction and is the closest to the two goals of large area growth and mass production of graphene.

In general, graphite oxide is readily dispersible in water (distilled water) and is present as a thin film plate (graphite oxide consisting of tens to hundreds of layers) negatively charged in a polar solvent. A stripping process is required to form the dispersed graphite oxide thin film plate with graphene oxide.

The most widely used exfoliation method is ultrasonicagitation, and there is a method of separating the layer of expanded graphite oxide through rapid heating. Graphite oxide is made in the form of a brown viscous slurry and is formed from graphite oxide, a stripped thin film oxidation plate, a piece of unoxidized graphite, and residues of oxidizing agent. Graphite oxide is subjected to purification through centrifugation and the like. The refined graphite oxide is peeled off in the form of graphene oxide through ultrasonic treatment.

Hereinafter, the method of forming graphene oxide will be described in more detail. However, the method of synthesizing graphene oxide is not limited to the method described later.

Graphite, H 2 SO 4 , K 2 S 2 O 8 and P 2 O 5 are mixed with stirring at a temperature higher than room temperature (for example, 60 to 99 ° C). Wherein the K 2 S 2 O 8 and P 2 O 5 are mixed in a weight ratio of 1: 0.1 to 10, and the H 2 SO 4 is mixed with the total content of K 2 S 2 O 8 and P 2 O 5 by 1 : 1 to 20 by volume. The resultant mixture is reacted at a temperature higher than room temperature by using a hot plate or the like. The temperature is preferably about 60 to about 99 DEG C, and the reaction is preferably performed for about 1 to about 48 hours.

Cool the resulting mixture to room temperature, add distilled water, and allow to stand. It is preferable that the abovementioned leaving is performed for about 6 to 72 hours.

The precipitate is selectively separated from the neglected result.

Selective precipitate is washed with distilled water to remove remaining acid or base. The precipitate is dispersed in distilled water and H 2 SO 4 and KMnO 4 are added. H 2 SO 4 and KMnO 4 are preferably added slowly at a temperature lower than room temperature (for example, -5 ° C to 4 ° C).

Add H 2 SO 4 and KMnO 4 to distilled water and add H 2 O 2 to distilled water to make the solution yellow.

The precipitate is selectively separated from the solution which turns bright yellow. Selective precipitate is washed with distilled water to remove remaining acid or base. In this way, graphite oxide can be obtained.

The graphite oxide is peeled off in a polar solvent using ultrasonic waves to form a graphene oxide dispersion. The graphite oxide is peeled off by ultrasonic treatment to obtain a graphene oxide dispersion. The graphene oxide may be in the form of a single layer, a bilayer, or a multilayer. The polar solvent may be an amide type such as dimethylformamide (DMF), a pyrrolidone type such as N-methylpyrrolidone (NMP), an alcohol type such as ethanol, a dimethylsulfoxide ; DMSO), nitrile such as acetonitrile, ketone such as acetone, tetrahydrofuran (THF), ether such as diethylether, toluene (toluene) toluene, and 1,2-dichlorobenzene (DCB), it is more effective to use a solvent having a high polarity and particularly a hydrogen bond.

The activated carbon is oxidized in an acid solution containing an oxygen component. The activated carbon is preferably spherical activated carbon in consideration of improvement of specific surface area, coating of graphene, and the like. The acid solution is preferably an acid solution containing an oxygen component such as nitric acid (HNO 3 ), phosphoric acid (H 3 PO 4 ), sulfuric acid (H 2 SO 4 ), acetic acid (HCOOH). 1 is a view showing an oxidized activated carbon. In FIG. 1, only a part of the activated carbon 200 is shown. Oxygen functional groups are formed on the surface of the activated carbon 200 by the oxidation treatment with the acidic solution.

The oxidation-treated activated carbon is introduced into the graphene oxide dispersion to form a mixed dispersion of activated carbon-graphene oxide. The activated carbon-graphene oxide mixed dispersion preferably contains 1 to 30 parts by weight of graphene oxide per 100 parts by weight of the oxidized activated carbon.

The isocyanate compound is added to the activated carbon-graphen oxide mixed dispersion and mixed to form an isocyanate-introduced activated carbon-graphene oxide complex. The mixing is preferably performed at a temperature of about 40 to 80 DEG C for 1 to 48 hours. The isocyanate compound may include at least one material selected from isocyanate, diisocyanate and triisocyanate. The isocyanate compound reacts with an oxygen functional group on the surface of activated carbon or an oxygen functional group on the surface of graphene to form an isocyanate group. FIG. 2 is a view showing a state where an isocyanate group is formed by reacting with an oxygen functional group on the surface of activated carbon 200. In FIG. 2, only a part of activated carbon 200 is shown.

Unreacted diisocyanate is washed and vacuum filtered to selectively isolate the isocyanate-introduced activated carbon-graphene oxide complex.

The activated carbon-graphene oxide complex into which the isocyanate has been introduced is dispersed in a polar solvent, and an organic compound containing an amino group and a pyrimidine group is introduced and mixed in order to introduce a nitrogen functional group, . The mixing is preferably performed at a temperature of about 80 to 120 DEG C for 1 to 48 hours. The organic compound containing an amino group and a pyrimidine group may be 2-amino-4-hydroxy-6-methylpyrimidine, 2-amino-4,6-dimethylpyrimidine Amino-4-methylpyrimidine, 2-amino-4,6-dimethylpyrimidine and 2-amino-4-methylpyrimidine. The polar solvent may be an amide type such as dimethylformamide (DMF), a pyrrolidone type such as N-methylpyrrolidone (NMP), an alcohol type such as ethanol, a dimethylsulfoxide ; DMSO), nitrile such as acetonitrile, ketone such as acetone, tetrahydrofuran (THF), ether such as diethylether, toluene (toluene) toluene, and 1,2-dichlorobenzene (DCB), it is more effective to use a solvent having a high polarity and particularly a hydrogen bond.

The activated carbon - graphene oxide complex into which the nitrogen functional group is introduced is selectively separated by washing and vacuum filtration. The washing is preferably performed using distilled water or the like in order to neutralize the pH of the mixed material due to the acidic solution.

The activated carbon-graphene oxide complex into which the nitrogen functional group has been introduced is subjected to a reduction heat treatment to obtain an activated carbon-graphene composite (with nitrogen functional groups) doped with nitrogen. The reduction heat treatment is preferably performed at a temperature of 450 to 900 DEG C for 10 minutes to 12 hours in a nitrogen gas atmosphere. The graphene oxide is reduced to graphene by reduction heat treatment. The nitrogen-doped activated carbon-graphene composite (with nitrogen functional groups incorporated therein) thus prepared is useful as an electrode active material for ultracapacitors. Figure 3 is a view showing an activated carbon-graphene composite with nitrogen doping (with nitrogen functionality introduced). Graphene having a high specific surface area and excellent electrical conductivity is coated on the surface of the activated carbon 200 and is introduced as a nitrogen functional group onto the surface by an organic compound containing an amino group and a pyrimidine group.

Hereinafter, a method of manufacturing an ultracapacitor electrode using an electrode active material for an ultracapacitor will be described in detail.

An electrode active material for an ultracapacitor (nitrogen-doped activated carbon-graphene composite) and a binder are mixed in a dispersion medium to form a composition for a paste-like electrode.

It is preferable that the binder is mixed in an amount of 1 to 20 parts by weight based on 100 parts by weight of the electrode active material for the ultracapacitor. The binder may be selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), polyvinyl butyral polyvinyl butyral (PVB), poly-N-vinylpyrrolidone (PVP), styrene butadiene rubber (SBR), polyamide-imide, polyimide, And the like can be used alone or in combination.

The dispersion medium may be an organic solvent such as ethanol (EtOH), acetone, isopropyl alcohol, N-methylpyrrolidone (NMP), propylene glycol (PG) or water.

Since the electrode composition is in the paste form, uniform mixing (complete dispersion) may be difficult. When the mixture is stirred for a predetermined time (for example, 1 minute to 12 hours) using a mixer such as a high-speed mixer, Can be obtained.

The electrode composition is formed into an ultracapacitor electrode. The electrode composition may be formed into an electrode shape by pressing the electrode composition, or may be formed into an electrode shape by coating the electrode composition with a metal foil. Alternatively, the electrode composition may be rolled into a sheet state, .

More specifically explaining an example of formation in an electrode form, the electrode composition can be pressed (rolled) by using a roll press molding machine. The roll press molding machine aims at improving the electrode density through rolling and controlling the thickness of the electrode. The roll press molding machine includes a controller capable of controlling the thickness and the heating temperature of the rolls and rolls at the upper and lower ends, the winding ≪ / RTI > As the electrode in the roll state passes the roll press, the rolling process is carried out and the roll is rolled again to complete the electrode. At this time, the pressing pressure of the press is preferably 1 to 20 ton / cm 2, and the roll temperature is preferably 40 to 150 캜.

The electrode-shaped molding is dried. The drying is preferably performed in a vacuum atmosphere at a temperature of 120 ° C to 350 ° C. The drying is preferably carried out at the above temperature for about 10 minutes to 48 hours. Such a drying process improves the strength of the ultracapacitor electrode while drying (evaporating the dispersion medium) the composition for a molded electrode.

The ultracapacitor electrode manufactured as described above can be applied to a small coin type ultracapacitor with a high capacity.

4 is a sectional view of a coin type ultracapacitor cell to which the ultracapacitor electrode 10 is applied, according to an embodiment of the present invention. Reference numeral 190 denotes a case (or a metal cap). Reference numeral 160 denotes a porous separator for preventing insulation and short-circuiting between the anode 120 and the cathode 110. Reference numeral 192 denotes a separator It is a gasket to prevent leakage and to prevent insulation and short circuit. At this time, the anode 120 and the cathode 110 are firmly fixed to the case (or metal cap) 190 by an adhesive.

The coin-type ultracapacitor cell includes an anode 120 made of the above-described ultracapacitor electrode, a cathode 110 made of the above-described ultracapacitor electrode, a cathode 110 disposed between the anode 120 and the cathode 110, A separator 160 for preventing a short circuit between the anode 120 and the cathode 120 is disposed in a case (or a metal cap) 190 and an electrolyte solution in which an electrolyte is dissolved between the anode 120 and the cathode 110 And then sealing with a gasket 192. [0064]

The separator may be a battery such as a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyester nonwoven fabric, a polyacrylonitrile porous separator, a poly (vinylidene fluoride) hexafluoropropane copolymer porous separator, a cellulose porous separator, a kraft paper or a rayon fiber, And is not particularly limited as long as it is a membrane commonly used in the field.

On the other hand, the electrolyte charged in the ultracapacitor is mixed with at least one solvent selected from the group consisting of propylene carbonate (PC), acetonitrile (AN) and sulfolane (SL), tetraethylammonium tetrafluoborate (TEABF4) and triethylmethylammonium tetrafluoborate ) May be used. The electrolytic solution may contain at least one ionic liquid selected from 1-ethyl-3-methyl imidazolium tetrafluoroborate (EMIBF4) and 1-ethyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide.

5 to 8 are views showing an ultracapacitor cell according to another example, and a method of manufacturing the ultracapacitor cell will be described in detail with reference to FIGS. 5 to 8. FIG.

As shown in FIG. 5, lead wires 130 and 140 are attached to an anode 120 and a cathode 110, respectively, which are ultracapacitor electrodes.

6, the first separator 150, the anode 120, the second separator 160, and the working electrode 110 are laminated and coiled to form a roll- (175), and wound around the roll with an adhesive tape (170) or the like so that the roll shape can be maintained.

The second separator 160 between the anode 120 and the cathode 110 prevents shorting between the anode 120 and the cathode 110. The first and second separation membranes 150 and 160 may be formed of any one of a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyester nonwoven fabric, a polyacrylonitrile porous separator, a poly (vinylidene fluoride) hexafluoropropane copolymer porous separator, a cellulose porous separator, Or a separator commonly used in the field of batteries and capacitors such as rayon fibers.

7, a sealing rubber 180 is mounted on the resultant roll, and the sealing rubber 180 is inserted into a case (or a metal cap) (for example, an aluminum case (Al Case) 190) .

The electrolytic solution is injected and sealed so that the roll-shaped winding element 175 (or the anode 120 and the cathode 110) is impregnated. The electrolytic solution may contain at least one selected from the group consisting of tetraethylammonium tetrafluoroborate (TEABF4) and triethylmethylammonium tetrafluoborate (TEABF4) in at least one solvent selected from the group consisting of propylene carbonate (PC), acetonitrile (AN) and sulfolane A solution in which a salt is dissolved can be used. The electrolytic solution may contain at least one ionic liquid selected from 1-ethyl-3-methyl imidazolium tetrafluoroborate (EMIBF4) and 1-ethyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide.

The ultracapacitor cell thus manufactured is schematically shown in Fig.

Hereinafter, experimental examples according to the present invention will be specifically shown, and the present invention is not limited to the following experimental examples.

<Experimental Example>

Natural graphite of 3g (150㎛, Sigma Aldrich), H 2 SO 4 of 12㎖ (95%, Samchun Chemicals), of 2.5g K 2 S 2 O 8 (Sigma-Aldrich) and 2.5g of P 2 O 5 (Sigma Aldrich) were mixed and stirred at 80 DEG C for 5 hours. The mixture was then cooled to room temperature, 500 ml of distilled water was added slowly and allowed to stand for 24 hours.

The precipitate separated from the mixture was washed with distilled water to remove remaining acids and salts, and then dispersed in distilled water. Then, while maintaining the temperature at 0 ° C, 120 ml of H 2 SO 4 and 15 g of KMnO 4 (Sigma Aldrich) was slowly added in turn.

After the mixture containing H 2 SO 4 and KMnO 4 was stirred at 35 ° C for 2 hours, 250 ml of distilled water was added slowly. Stirring was continued for another 2 hours and 700 ml of distilled water was added.

20 mL of H 2 O 2 (34.5%) was added to the mixture to which distilled water had been added. As the foaming occurred, the color of the solution changed to a bright yellow color.

A precipitate was obtained from the yellow solution and washed with 10% HCl (v / v) and distilled water to obtain graphite oxide.

1 g of the synthesized graphite oxide was separated by ultrasonication in 800 ml of dimethylformamide for 30 minutes in an argon (Ar) atmosphere to prepare a graphene oxide dispersion.

The spherical activated carbon was oxidized for 12 hours in 300 ml of HNO 3 (60%, Samcheon Chemical) solution, and 9 g of the oxidized activated carbon was added to the graphene oxide dispersion to prepare an activated carbon-graphene oxide mixed dispersion.

To prepare a material containing an isocyanate group by reacting a diisocyanate with an oxygen functional group on the surface of activated carbon or an oxygen functional group on the surface of graphene, 4 ml of diisocyanate (TDI, Sigma Aldrich) was added to a mixed dispersion of activated carbon- , And mixed at 50 DEG C for 24 hours.

In order to neutralize the pH of the mixed material due to the acidic solution, an activated carbon-graphene oxide complex having an isocyanate introduced therein was prepared by washing with distilled water and performing a vacuum filter. Then, 800 ml of dimethylformamide (Junsei) And 1.8 g of 2-amino-4-hydroxy-6-methyl-pyrimidine (AHMP, Sigma Aldrich) was added thereto to introduce nitrogen functional groups And mixed at 100 DEG C for 20 hours.

The activated carbon-graphene oxide complex thus prepared was subjected to washing and vacuum filtration, and subjected to a reduction heat treatment at 500 ° C. for 1 hour under a nitrogen atmosphere at 300 cc / min to produce an activated carbon-graphene composite having a nitrogen functional group introduced therein .

The activated carbon-graphene complex into which the nitrogen functional group was introduced was added to 25 ml of anhydrous ethanol together with the binder, and the mixture was stirred at a high speed for 10 minutes at a speed of 2000 rpm using a high-speed mixer to prepare a paste composition. The composite and the binder (PTFE) were added in a weight ratio of 95: 5. Polytetrafluoroethylene (PTFE) was used as the binder.

The kneaded composition for electrode was molded in a roll press molding machine until the surface became smooth. The roll press molding machine includes an upper roll and a lower roll, and the composition for electrode is passed between the upper roll and the lower roll to form the roll. The resultant product passed between the upper roll and the lower roll was folded in half, and the process of passing the upper product between the upper roll and the lower roll was repeated 15 times to obtain a composition sheet for a electrode having a smooth surface. The pressure applied to the electrode composition was about 10 ton / cm 2, and the heating temperature was about 60 ° C. The electrode composition sheet had a thickness of about 150 mu m.

The electrode composition sheet was dried in a dryer at 150 캜 for 6 hours to obtain an ultracapacitor electrode. The drying was performed in a vacuum atmosphere.

The ultracapacitor electrode thus manufactured was punched to a size of 12 mm and used as an anode and a cathode of an ultracapacitor.

The ultracapacitor was assembled into a full cell with a coin type (2032) cell. The membrane used was TF4035 from NKK. The electrolytic solution was prepared by dissolving 1 M of TEABF 4 in an acetonitrile solvent.

The ultracapacitor thus prepared was subjected to aging at a voltage of 60 DEG C and a voltage of 2.7 V. After the aging, charging and discharging were performed from 1 V to 2.7 V at room temperature to measure the capacity per volume.

9 is a scanning electron microscope (SEM) photograph showing the shape of the nitrogen-doped activated carbon-graphene composite prepared according to the experimental example.

10 is an N1s XPS (X-ray Photoelectron Spectroscopy) analysis graph of the nitrogen-doped activated carbon-graphene composite prepared according to Experimental Example.

A comparative example is presented to more easily grasp the characteristics of the above experimental example.

<Comparative Example>

The same activated carbon as used in the Experimental Example was prepared.

Activated carbon, a conductive material, a binder and a dispersion medium were mixed to form an ultracapacitor electrode. This will be described in more detail.

The activated carbon, the conductive material and the binder were added to 25 ml of anhydrous ethanol as a dispersion medium, and the mixture was stirred at a high speed for 10 minutes at a speed of 2000 rpm using a high-speed mixer to prepare a paste composition. The activated carbon, the conductive material and the binder were added in a weight ratio of 95: 5: 5. The conductive material used was Super-P. Polytetrafluoroethylene (PTFE) was used as the binder.

The kneaded composition for electrode was molded in a roll press molding machine until the surface became smooth. The roll press molding machine includes an upper roll and a lower roll, and the composition for electrode is passed between the upper roll and the lower roll to form the roll. The resultant product passed between the upper roll and the lower roll was folded in half, and the process of passing the upper product between the upper roll and the lower roll was repeated 15 times to obtain a composition sheet for a electrode having a smooth surface. The pressure applied to the electrode composition was about 10 ton / cm 2, and the heating temperature was about 60 ° C. The electrode composition sheet had a thickness of about 150 mu m.

The electrode composition sheet was dried in a dryer at 150 캜 for 6 hours to obtain an ultracapacitor electrode. The drying was performed in a vacuum atmosphere.

The ultracapacitor electrode thus manufactured was punched to a size of 12 mm and used as an anode and a cathode of an ultracapacitor.

The ultracapacitor was assembled into a full cell with a coin type (2032) cell. The membrane used was TF4035 from NKK. The electrolytic solution was prepared by dissolving 1 M of TEABF 4 in an acetonitrile solvent.

The ultracapacitor thus prepared was subjected to aging at a voltage of 60 DEG C and a voltage of 2.7 V. After the aging, charging and discharging were performed from 1 V to 2.7 V at room temperature to measure the capacity per volume.

11 is a graph showing discharge curves of an ultracapacitor manufactured according to Experimental Examples and Comparative Examples.

Referring to FIG. 11, the discharging characteristics of the ultracapacitor manufactured according to the experimental example are superior to those of the ultracapacitor manufactured according to the comparative example.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, This is possible.

110: cathode 120: anode
130: first lead wire 140: second lead wire
150: first separator 160: second separator
170: Adhesive tape 175: Winding element
180: sealing rubber 190: case
192: gasket 200: activated carbon

Claims (12)

A method of manufacturing an electrode active material for an ultra-capacitor,
Forming a graphite oxide;
Introducing the graphite oxide into a polar solvent, and peeling the graphite oxide by ultrasonic treatment to form a graphene oxide dispersion;
Oxidizing the activated carbon in an acid solution containing an oxygen component;
Introducing the oxidized activated carbon into the graphene oxide dispersion to form an activated carbon-graphene oxide mixed dispersion;
Introducing an isocyanate compound into the activated carbon-graphene oxide mixed dispersion to form an isocyanate-introduced activated carbon-graphene oxide complex;
Dispersing the activated carbon-graphene oxide complex into which the isocyanate is introduced in a polar solvent, and introducing an organic compound containing an amino group and a pyrimidine group to form an activated carbon-graphene oxide complex into which a nitrogen functional group is introduced; And
And a step of reducing heat treatment of the activated carbon-graphene oxide complex into which the nitrogen functional group has been introduced to obtain a nitrogen-doped activated carbon-graphene composite.
The method of claim 1, wherein forming the graphite oxide comprises:
Mixing graphite, H 2 SO 4 , K 2 S 2 O 8 and P 2 O 5 with stirring;
Cooling the resultant mixture to room temperature, adding distilled water and allowing it to stand;
Selectively separating the precipitate from the neglected result;
Dispersing the selectively separated precipitate in distilled water, adding H 2 SO 4 and KMnO 4 ;
Adding H 2 O 2 to the solution to which distilled water has been additionally added to the resultant of addition of H 2 SO 4 and KMnO 4 , thereby changing the color of the solution to a bright yellow color as the foaming occurs; And
And selectively separating the precipitate from the solution turned into a light yellow color.
The method according to claim 1, wherein the isocyanate compound comprises at least one material selected from the group consisting of isocyanate, diisocyanate, and triisocyanate.
The organic compound according to claim 1, wherein the amino group and the pyrimidine group are contained in the organic compound,
2-amino-4-hydroxy-6-methylpyrimidine, 2-amino-4,6-dimethylpyrimidine, And 2-amino-4-methylpyrimidine. 2. The method for producing an electrode active material for an ultra-capacitor according to claim 1,
The method according to claim 1, wherein the activated carbon-graphen oxide mixed dispersion contains 1 to 30 parts by weight of graphene oxide per 100 parts by weight of the oxidized activated carbon.
The method of claim 1, wherein the reducing heat treatment is performed at a temperature of 450 to 900 占 폚 in a nitrogen gas atmosphere.
Forming a graphite oxide;
Introducing the graphite oxide into a polar solvent, and peeling the graphite oxide by ultrasonic treatment to form a graphene oxide dispersion;
Oxidizing the activated carbon in an acid solution containing an oxygen component;
Introducing the oxidized activated carbon into the graphene oxide dispersion to form an activated carbon-graphene oxide mixed dispersion;
Introducing an isocyanate compound into the activated carbon-graphene oxide mixed dispersion to form an isocyanate-introduced activated carbon-graphene oxide complex;
Dispersing the activated carbon-graphene oxide complex into which the isocyanate is introduced in a polar solvent, and introducing an organic compound containing an amino group and a pyrimidine group to form an activated carbon-graphene oxide complex into which a nitrogen functional group is introduced;
Obtaining a nitrogen-doped activated carbon-graphene composite by reducing heat treatment of the activated carbon-graphene oxide complex into which the nitrogen functional group is introduced;
Mixing the nitrogen-doped activated carbon-graphene composite, which is an electrode active material for an ultracapacitor, with a binder in a dispersion medium to form a composition for a paste-like electrode;
Molding the electrode composition into an ultracapacitor electrode; And
And drying the electrode-shaped molding to form an ultracapacitor electrode.
The method according to claim 7, wherein the binder is mixed in an amount of 1 to 20 parts by weight based on 100 parts by weight of the electrode active material for the ultracapacitor.
8. The method of claim 7,
Rolling the electrode composition using a roll press molding machine to form a sheet type electrode,
The pressure applied to the electrode composition by the roll press molding machine is in the range of 1 to 20 ton /
The heating temperature applied to the electrode composition is in the range of 40 to 150 占 폚,
Wherein the electrode of the sheet type has an average thickness of 100 to 300 mu m.
The method according to claim 7, wherein the drying is performed in a vacuum atmosphere at a temperature of 120 to 350 캜.
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