KR101771012B1 - Lithium ion doping method for ultra capacitor - Google Patents

Lithium ion doping method for ultra capacitor Download PDF

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KR101771012B1
KR101771012B1 KR1020150034199A KR20150034199A KR101771012B1 KR 101771012 B1 KR101771012 B1 KR 101771012B1 KR 1020150034199 A KR1020150034199 A KR 1020150034199A KR 20150034199 A KR20150034199 A KR 20150034199A KR 101771012 B1 KR101771012 B1 KR 101771012B1
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positive electrode
negative electrode
weight
lithium
cathode
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KR1020150034199A
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Korean (ko)
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KR20160109550A (en
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노광철
박선민
김목화
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한국세라믹기술원
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    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • 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 of manufacturing a positive electrode, comprising the steps of: preparing a positive electrode having a structure in which a positive electrode material containing a positive electrode active material is applied to one surface or both surfaces of a current collector having a plurality of holes penetrating the top and bottom surfaces; Comprising the steps of: preparing a negative electrode having a structure coated on one surface or both surfaces of a current collector having a plurality of holes passing through a rim surface; preparing an electrolyte solution in which a lithium salt and a lithium metal are dissolved in a non-aqueous solvent; A cathode, and a separator disposed between the anode and the cathode, the separator being disposed in the metal cap to prevent shorting between the anode and the cathode, and the electrolyte is injected so as to impregnate the anode and the cathode, And applying a voltage to the metal cap to perform a first charge process, wherein the first charge process And lithium from the lithium metal and the lithium salt is doped on the surface and inside of the graphite. The present invention also relates to a lithium ion doping method of an ultracapacitor. According to the present invention, lithium can be doped into the cathode of an ultracapacitor by the lithium metal previously dissolved in the electrolyte in the first charging process without a separate pre-doping step, and the capacitance characteristics of the ultracapacitor and stable Charge and discharge characteristics can be provided.

Description

[0001] The present invention relates to a lithium ion doping method for ultra capacitors,

The present invention relates to a lithium ion doping method of an ultracapacitor, and more particularly, it relates to a lithium ion doping method of an ultracapacitor, in which lithium can be doped into a cathode of an ultracapacitor by lithium metal previously dissolved in an electrolyte during a first charging process without a separate pre- The present invention relates to a lithium ion doping method of an ultracapacitor capable of providing capacity characteristics and stable charge / discharge characteristics of an ultracapacitor.

Generally, an ultracapacitor uses an electrode and a conductor, and a pair of charge layers (electric double layer) having different signs at the interface of the electrolyte solution impregnated with the electrode and the conductor, so that deterioration due to repeated charge / It is small and requires no maintenance. 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 includes 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 insulation and short circuit, A gasket for preventing leakage of electricity and preventing insulation and short-circuit, and a metal cap as a conductor for packaging them. Then, one or more unit cells (normally 2 to 6 in the case of the coin type) are stacked in series and the two terminals of the positive and negative electrodes are combined.

Background Art [0002] Carbon materials such as graphite are most widely used as active materials for the positive and negative electrodes of capacitors. The carbon material has fast charge / discharge and long life characteristics.

Ultracapacitors using graphite as the cathode and activated carbon as the anode have difficulties in increasing the energy density of the capacitor due to the limitation of the operating voltage.

Korean Patent Registration No. 10-1296224

The problem to be solved by the present invention is that lithium can be doped into the cathode of the ultracapacitor by the lithium metal previously dissolved in the electrolyte in the first charging process without a separate pre-doping step, Discharge characteristics of an ultracapacitor capable of providing a discharge characteristic.

The present invention relates to a method of manufacturing a positive electrode, comprising the steps of: preparing a positive electrode having a structure in which a positive electrode material containing a positive electrode active material is applied to one surface or both surfaces of a current collector having a plurality of holes penetrating the top and bottom surfaces; Comprising the steps of: preparing a negative electrode having a structure coated on one surface or both surfaces of a current collector having a plurality of holes passing through a rim surface; preparing an electrolyte solution in which a lithium salt and a lithium metal are dissolved in a non-aqueous solvent; A cathode, and a separator disposed between the anode and the cathode, the separator being disposed in the metal cap to prevent shorting between the anode and the cathode, and the electrolyte is injected so as to impregnate the anode and the cathode, And applying a voltage to the metal cap to perform a first charge process, wherein the first charge process Lithium ions from the lithium metal and the lithium salt are doped on the surface and inside of the graphite.

The lithium salt is selected from the group consisting of LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 and LiAlO 4 and LiAlCl 4 And the lithium salt may be dissolved in the non-aqueous solvent at a concentration of 0.1 SIMILAR 5.0M.

It is preferable that 0.01 to 15.0 g of the lithium metal is dissolved in 10 ml of the non-aqueous solvent in which the lithium salt is dissolved.

The non-aqueous solvent may include acetonitrile.

The positive electrode is manufactured by mixing the activated carbon powder as the positive electrode active material, the conductive material, the binder and the dispersion medium to prepare a positive electrode material, coating the positive electrode material on one side or both sides of the current collector, And the positive electrode material may be prepared by mixing 2 to 20 parts by weight of the conductive material with 100 parts by weight of activated carbon powder and activated carbon powder and 2 to 20 parts by weight of the activated carbon powder 100 2 to 10 parts by weight of a binder and 200 to 300 parts by weight of a dispersion medium based on 100 parts by weight of an activated carbon powder.

The activated carbon powder preferably has a specific surface area of 1000 to 3000 m 2 / g, and the average particle size of the activated carbon powder is preferably 0.5 to 20 μm.

The negative electrode is manufactured by preparing a negative electrode material by mixing graphite powder, a conductive material, a binder and a dispersion medium, which is a negative electrode active material, coating the negative electrode material on one surface or both surfaces of the current collector, And the cathode material may include graphite powder, 2 to 20 parts by weight of a conductive material, 100 parts by weight of graphite powder 100, 100 parts by weight of graphite powder, 2 to 10 parts by weight of a binder with respect to 100 parts by weight of graphite powder and 200 to 300 parts by weight of a dispersion medium with respect to 100 parts by weight of graphite powder.

The graphite powder may include at least one selected from natural graphite, artificial graphite and soft carbon graphite, and the average particle size of the graphite powder is preferably 0.5 to 20 占 퐉.

Wherein the ultracapacitor may be a wound capacitor and the step of fabricating the ultracapacitor includes the steps of connecting a first lead wire to the cathode, connecting a second lead wire to the anode, 1 separator, a cathode, a second separator for preventing short-circuiting between the anode and the cathode, and the cathode are sequentially laminated and coiled to form a roll-like roll canceller, And injecting the electrolyte solution in which the lithium salt and the lithium metal are dissolved so as to impregnate the positive electrode and the negative electrode of the negative electrode, into the metal cap.

According to the present invention, lithium can be doped into the cathode of the ultracapacitor during the first charging process without using a separate pre-doping process using an electrolyte in which lithium metal is dissolved. Lithium can be doped into the cathode of the ultracapacitor by the lithium metal previously dissolved in the electrolyte in the first charging process without a separate pre-doping step, thereby providing capacity characteristics of the ultracapacitor and stable charging / discharging characteristics.

1 is a view showing a current collector 20 having a sheet 10 of a cathode material and a plurality of holes (openings) penetrating the front and back surfaces.
2 is a view showing a current collector 20 having a sheet 60 of a negative electrode material and a plurality of holes (openings) 50 penetrating the front and back surfaces.
3 is a cross-sectional view of a coin type ultracapacitor.
Figs. 4 to 7 are views showing a wound type ultracapacitor. Fig.
FIG. 8 is a graph showing the behavior of the first charging process, which is lithium ion pre-doping, of an ultracapacitor manufactured according to Experimental Examples and Comparative Examples.
9 is a graph showing charging / discharging efficiency and discharging capacity after pre-doping 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 present invention relates to a lithium ion doping method of an ultracapacitor, and more particularly, to a method of doping lithium into a cathode of an ultracapacitor during a first charge process without using a separate pre-doping process using an electrolyte in which lithium metal is dissolved will be.

According to the present invention, lithium can be doped into the cathode of the ultracapacitor by the lithium metal previously dissolved in the electrolyte during the first charging process without a separate pre-doping step, and the capacity and stable charge / discharge characteristics of the ultracapacitor .

A lithium ion doping method of an ultracapacitor according to a preferred embodiment of the present invention is a method of doping a positive electrode having a structure in which a positive electrode material containing a positive electrode active material is applied to one surface or both surfaces of a current collector having a plurality of holes penetrating the surface, A step of preparing a negative electrode having a structure in which a negative electrode material including a negative electrode active material is applied to one surface or both surfaces of a current collector having a plurality of holes passing through the top and bottom surfaces, And a separation membrane disposed between the anode and the cathode and for preventing a short circuit between the anode and the cathode is disposed in the metal cap, and the anode and the cathode Injecting the electrolytic solution so as to impregnate the metal cap, and sealing the ultracapacitor to manufacture an ultracapacitor; W performing a first charging process, and in the first charging process, the lithium comes from the lithium metal and the lithium salt is doped on the surface and in the interior of the graphite.

The lithium salt is selected from the group consisting of LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 and LiAlO 4 and LiAlCl 4 And the lithium salt may be dissolved in the non-aqueous solvent at a concentration of 0.1 SIMILAR 5.0M.

It is preferable that 0.01 to 15.0 g of the lithium metal is dissolved in 10 ml of the non-aqueous solvent in which the lithium salt is dissolved.

The non-aqueous solvent may include acetonitrile.

The positive electrode is manufactured by mixing the activated carbon powder as the positive electrode active material, the conductive material, the binder and the dispersion medium to prepare a positive electrode material, coating the positive electrode material on one side or both sides of the current collector, And the positive electrode material may be prepared by mixing 2 to 20 parts by weight of the conductive material with 100 parts by weight of activated carbon powder and activated carbon powder and 2 to 20 parts by weight of the activated carbon powder 100 2 to 10 parts by weight of a binder and 200 to 300 parts by weight of a dispersion medium based on 100 parts by weight of an activated carbon powder.

The activated carbon powder preferably has a specific surface area of 1000 to 3000 m 2 / g, and the average particle size of the activated carbon powder is preferably 0.5 to 20 μm.

The negative electrode is manufactured by preparing a negative electrode material by mixing graphite powder, a conductive material, a binder and a dispersion medium, which is a negative electrode active material, coating the negative electrode material on one surface or both surfaces of the current collector, And the cathode material may include graphite powder, 2 to 20 parts by weight of a conductive material, 100 parts by weight of graphite powder 100, 100 parts by weight of graphite powder, 2 to 10 parts by weight of a binder with respect to 100 parts by weight of graphite powder and 200 to 300 parts by weight of a dispersion medium with respect to 100 parts by weight of graphite powder.

The graphite powder may include at least one selected from natural graphite, artificial graphite and soft carbon graphite, and the average particle size of the graphite powder is preferably 0.5 to 20 占 퐉.

Wherein the ultracapacitor may be a wound capacitor and the step of fabricating the ultracapacitor includes the steps of connecting a first lead wire to the cathode, connecting a second lead wire to the anode, 1 separator, a cathode, a second separator for preventing short-circuiting between the anode and the cathode, and the cathode are sequentially laminated and coiled to form a roll-like roll canceller, And injecting the electrolyte solution in which the lithium salt and the lithium metal are dissolved so as to impregnate the positive electrode and the negative electrode of the negative electrode, into the metal cap.

Hereinafter, an ultracapacitor cell according to a preferred embodiment of the present invention and a method of manufacturing the same will be described in more detail.

The electrolytic solution of the ultracapacitor uses a non-aqueous electrolytic solution in which a lithium salt and a lithium metal are dissolved.

As the solvent constituting the electrolyte, acetonitrile (ACN) may be used as a non-aqueous solvent capable of dissolving lithium metal.

The lithium salt is LiPF 6, LiBF 4, LiSbF 6 , LiAsF 6, LiClO 4, LiCF 3 SO 3, LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2 and LiAlO 4, LiAlCl 4, or And mixtures thereof. It is preferable that the lithium salt is dissolved in the non-aqueous solvent at a concentration of about 0.1 to 5.0M.

It is preferable that 0.01 to 15.0 g of the lithium metal is dissolved in 10 ml of the non-aqueous solvent in which the lithium salt is dissolved.

The anode 120 of the ultracapacitor uses an electrode formed by applying a positive electrode material containing activated carbon to the current collector. The anode 120 has a structure in which a cathode material containing activated carbon is formed on one surface or both surfaces of a current collector having a plurality of holes (openings) penetrating the front and back surfaces. 1 is a view showing a current collector 20 having a sheet 10 of a cathode material and a plurality of holes (openings) penetrating the front and back surfaces.

Hereinafter, a method of manufacturing the anode 120 of the ultracapacitor of the present invention will be described in detail.

Activated carbon powder, a conductive material, a binder and a dispersion medium to prepare a positive electrode material containing activated carbon. 2 to 20 parts by weight of the conductive material and 100 to 2 parts by weight of the active carbon powder are added to the activated carbon powder and 100 parts by weight of the activated carbon powder and 2 to 10 parts by weight of the binder are added to 100 parts by weight of the activated carbon powder, Preferably from 200 to 300 parts by weight.

The activated carbon powder is not particularly limited, and activated carbon used for general electrode production can be used. For example, coconut shell-based activated carbon, phenol resin-based activated carbon, and the like can be used. The specific surface area of the activated carbon powder used is preferably 1000 to 3000 m < 2 > / g. The average particle size of the activated carbon powder is preferably in the range of 0.5 to 20 占 퐉 in order to facilitate electrode formation and dispersion.

The conductive material is not particularly limited as long as it is an electron conductive material that does not cause a chemical change. Examples of the conductive material include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder such as copper, nickel, Fiber and the like.

The binder may be selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidenefluoride (PVdF), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), polyvinyl butyral vinyl butyral (PVB), poly-N-vinylpyrrolidone (PVP), styrene butadiene rubber (SBR), and the like.

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

The positive electrode material containing the activated carbon is coated on one side or both sides of a current collector having a plurality of openings (openings) penetrating the front and back surfaces, and dried to produce the positive electrode 120, State (rubber type) and attached to one side or both sides of the current collector or pressed to form the anode 120. 1 is a view showing a current collector 20 having a sheet of positive electrode material 10 made by pushing a positive electrode material with a roller and a plurality of holes (openings) 50 penetrating the front and back surfaces.

The current collector 20 having a plurality of holes (openings) 50 penetrating the front and back surfaces has a sieve shape including a plurality of frames and holes (openings) 50 that are empty spaces between the frames . The current collector 20 may include a plurality of first frames 30 arranged in a first direction and a plurality of second frames 40 arranged in a second direction.

1, a plurality of first frames 30 arranged in a first direction, a plurality of second frames 40 arranged in a second direction perpendicular to the first direction, The first frame 30 arranged in the first direction and the second frame 40 arranged in the second direction form a grid of a grid shape. The interval between the first frames 30 arranged in the first direction and the intervals between the second frames 40 arranged in the second direction may be different from each other. However, in the first frame 30 arranged in the first direction, The interval between the first frames 30 and the second frames 40 arranged in the second direction are preferably the same in terms of improvement of the bonding strength with the cathode material and uniform voltage application. Although the first frame 30 and the second frame 40 may have different line widths, the same line width is preferable in terms of improvement of the bonding strength with the cathode material, uniform voltage application, and the like. The first frame 30 and the second frame 40 may be arranged periodically or non-periodically. However, the periodic arrangement of the first frame 30 and the second frame 40 may improve adhesion strength with the cathode material, .

The size of the hole (opening) of the current collector 20 is preferably in the range of 0.1 to 2 mm in terms of improvement of the bonding strength with the cathode material, uniform voltage application, and the like. As shown in the figure, the frame 30 and 40 may have a square shape, but various shapes such as a rectangle, a rhombus, and a circle may be formed depending on the shapes of the frames 30 and 40.

The aperture ratio of the current collector 20 for manufacturing the anode 120 is preferably about 30 to 80% with respect to the total area of the current collector 20 in terms of uniform voltage application.

The frames 30 and 40 of the current collector 20 may be made of a metal material such as aluminum (Al), copper (Cu), titanium (Ti), or nickel (Ni) have.

The cathode 110 of the ultracapacitor of the present invention uses an electrode formed by applying a negative electrode material containing graphite to a current collector. The cathode 110 has a structure in which a negative electrode material including graphite is formed on one surface or both surfaces of a current collector having a plurality of openings (apertures) penetrating the front and back surfaces. 2 is a view showing a current collector 20 having a sheet 60 of a negative electrode material and a plurality of holes (openings) 50 penetrating the front and back surfaces.

Hereinafter, a method for manufacturing the cathode 10 of the ultracapacitor of the present invention will be described in detail with reference to FIG.

A graphite powder, a binder, a conductive material and a dispersion medium are mixed to prepare a negative electrode material.

The amount of the negative electrode material is preferably 2 to 20 parts by weight of the conductive material and 2 to 10 parts by weight of the binder with respect to 100 parts by weight of the graphite powder. The content of the dispersion medium is not particularly limited, but is preferably 200 to 300 parts by weight based on 100 parts by weight of the graphite powder.

The graphite powder is not particularly limited, and graphite used for general electrode production can be used. As the graphite powder to be used, it is preferable to use natural graphite, artificial graphite, soft carbon graphite or the like. The average particle size of the graphite powder is preferably in the range of 0.5 to 20 占 퐉 in order to facilitate electrode formation and dispersion.

The conductive material is not particularly limited as long as it is an electron conductive material that does not cause chemical changes. Examples of the conductive material include carbon black, acetylene black, ketjen black, carbon fiber, metal powder such as copper, nickel, aluminum and silver, or metal fiber.

The binder may be selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidenefluoride (PVdF), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), polyvinyl butyral polyvinyl butyral (PVB), poly-N-vinylpyrrolidone (PVP), styrene butadiene rubber (SBR), and the like.

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

The negative electrode material containing the graphite is coated on one side or both sides of a current collector having a plurality of holes (openings) penetrating the front and back surfaces as described above, and dried to manufacture the negative electrode 110, And may be made into a sheet state (rubber type) and adhered to or pressed on one surface or both surfaces of the current collector to produce a cathode 110. At this time, the aperture ratio of the current collector 20 for manufacturing the cathode 110 is preferably about 30 to 70% with respect to the total area of the current collector 20 in terms of uniform voltage application.

The ultracapacitor 100 is manufactured using the anode 120 and the cathode 110 manufactured as described above. Hereinafter, a method of manufacturing the ultracapacitor 100 will be described.

3 is a cross-sectional view of a coin type ultracapacitor. 3, reference numeral 190 denotes a metal cap as a conductor, 160 denotes a porous separator for insulation and short circuit between the anode 120 and the cathode 110, 192 denotes leakage of the electrolyte And to prevent insulation and short circuit. At this time, the anode 120 and the cathode 110 are firmly fixed by the metal cap 190 and an adhesive.

The coin-type ultracapacitor includes the above-described anode 120, the above-described cathode 110, and a cathode 120 disposed between the anode 120 and the cathode 110 to prevent a short circuit between the anode 120 and the cathode 120 A separator 160 is disposed in the metal cap 190 and an electrolytic solution in which an electrolyte is dissolved is injected between the anode 120 and the cathode 110 and then sealed with a gasket 192 have.

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.

Figs. 4 to 7 are views showing a wound type ultracapacitor. Fig.

As shown in FIG. 4, lead wires 130 and 140 are attached to the cathode 110 and the anode 120, respectively.

5, the first separator 150, the anode 120, the second separator 160, and the cathode 110 are laminated and coiled to form a roll- 175, and then rolled around the roll with the 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 the anode 120 and the cathode 110 from being short-circuited. 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, But is not particularly limited as long as it is a separator commonly used in the field of batteries and capacitors such as kraft paper or rayon fiber.

As shown in Fig. 6, a sealing rubber 180 is mounted on a roll-shaped resultant and is mounted on a metal cap (for example, an aluminum case (Al Case) 190).

The above-described electrolyte is injected and sealed so that the anode 120 and the cathode 110 of the roll-shaped winding element 175 are impregnated. The electrolytic solution is an electrolytic solution in which a lithium salt and lithium metal are dissolved.

The cell thus fabricated is schematically shown in Fig. 7, and the cell can be used as an ultracapacitor.

Hereinafter, a method of doping lithium on the surface and inside of the cathode in the ultracapacitor 100 will be described.

When a voltage is applied to the metal cap 190 to start the first charging process, lithium is doped (electrodeposited) on the surface of the graphite forming the cathode 110. The metal metal dissolved in the electrolyte reaches the graphite surface and is doped on the surface of the graphite and lithium from the lithium salt contained in the electrolyte reaches the graphite surface and is doped on the surface of the graphite. The lithium metal dissolved in the electrolyte acts as a source of lithium in doping graphite with lithium and also acts as a source of lithium in the lithium salt contained in the electrolytic solution in doping graphite with lithium. The positive electrode 120 and the negative electrode 110 are manufactured using the current collector 20 having a plurality of holes (openings) penetrating the front and back surfaces. Therefore, lithium ions can smoothly flow through the openings 50 of the current collector 20 So that penetration of lithium ions can be smoothly carried out even in the central portion of the graphite.

Lithium doped with graphite by the first charging process drops the negative electrode potential in an ultracapacitor using graphite as a cathode 110, so that intercalation and deintercalation occur rapidly during charging and discharging. The ultracapacitor 100 has a high energy density per unit volume due to the insertion and desorption of doped lithium on the surface of the graphite. The graphite constituting the cathode 110 has numerous pores. In the initial charging process, lithium is not doped only on the surface of the graphite, but rather along the pores connected to the inside or the vulk, Doping is also performed. In this way, lithium is doped not only on the surface of the graphite but also on the bulk (interior), so that insertion and desorption processes occur even in the bulk of the graphite during charging and discharging. When lithium is doped on the surface of the graphite forming the cathode, the cathode potential will be lowered, and the capacity of the ultracapacitor is increased by insertion and desorption of the doped lithium on the surface of the graphite.

It is possible to realize an ultracapacitor that realizes a high energy density per unit volume by using a negative electrode including lithium-doped graphite.

As described above, lithium can be doped into the cathode during the first charging process without using a separate pre-doping process by using an electrolyte in which lithium metal is dissolved. Lithium can be doped into the cathode by the lithium metal previously dissolved in the electrolyte during the first charging process without a separate pre-doping step, thereby providing capacity characteristics and stable charge / discharge characteristics of the ultracapacitor.

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 1>

0.2 g of lithium metal was dissolved in 50 ml of a 1.0 M LiBF 4 / ACN electrolyte solution, dispersed for 30 minutes, and then used as an electrolytic solution.

MSP20 (Kansai Coke & Chemicals Co.), a pulmonary activated carbon, was used as a cathode active material. MSP20 having a particle size of 0.9 to 20 占 퐉 and 5.5 parts by weight of a conductive material Ketjen Black (manufactured by Mitsubishi Chemical Co., Ltd., Japan) were mixed with 100 parts by weight of MSP20. Separately, 2.2 parts by weight of carboxymethyl cellulose (CMC) was added to distilled water to 100 parts by weight of MSP20 and mixed. Then, the two mixtures were put into a planetary mixer (manufactured by TK, model: Hivis disper) and dispersed by stirring for 1 hour. 3.3 parts by weight of styrene butadiene rubber (SBR) was added to 100 parts by weight of MSP20, Lt; / RTI &gt; to obtain a positive electrode material.

Next, the positive electrode material is coated on one surface of a current collector made of aluminum (Al) and having a first frame arranged in a first direction and a second frame arranged perpendicularly to the first direction and having an aperture ratio of about 40% And dried to prepare a positive electrode having a thickness of about 200 mu m.

PAC2 (Aekyung Petrochemical Co. LTD) was used as an anode active material. PAC2 having a particle size of 0.9 to 20 占 퐉 and 5.5 parts by weight of Ketjen Black (manufactured by Mitsubishi Chemical Co., Ltd., Japan) as a conductive material were mixed with 100 parts by weight of PAC2. Separately, 2.2 parts by weight of carboxymethylcellulose (CMC) was added to distilled water to 100 parts by weight of PAC2 and mixed. Then, the two mixtures were put into a planetary mixer (manufactured by TK, model: Hivis disper) and dispersed by stirring for 1 hour. 3.3 parts by weight of styrene butadiene rubber (SBR) was added to 100 parts by weight of PAC2, Lt; / RTI &gt; to obtain a negative electrode material.

Next, the negative electrode material is coated on one surface of a current collector made of copper (Cu) in a first frame arranged in a first direction and a second frame arranged in a direction perpendicular to the first direction and having an aperture ratio of about 40% And dried to produce a negative electrode having a thickness of about 50 mu m.

The weight ratio of the positive electrode and the negative electrode was such that the weight ratio of the positive electrode active material and the negative electrode active material was 2.5: 1.

The ultracapacitor was manufactured using a coin-shaped cell. The positive electrode was coated with a positive electrode material on an Al current collector, a negative electrode coated with a negative electrode material on a Cu current collector, and a separator was disposed between the positive electrode and the negative electrode. And an electrolyte solution in which the lithium salt and the lithium metal were dissolved was injected between the anode and the cathode and then sealed.

<Comparative Example>

An ultracapacitor was prepared in the same manner as in Experimental Example 1, except that a 1.0 M LiBF 4 / ACN electrolyte solution free from lithium metal was used.

FIG. 8 is a graph showing the behavior of the first charging process, which is lithium ion pre-doping, of an ultracapacitor manufactured according to Experimental Examples and Comparative Examples. 8 (a) is for an ultracapacitor manufactured according to the experimental example, and (b) is for an ultracapacitor manufactured according to a comparative example.

Referring to FIG. 8, the difference between the slope and the flat potential in the first charging process can be seen. The results of the experimental example show that the flat potential is more persistent than that of the comparative example. This phenomenon occurs when lithium ions in the electrolyte are doped into the negative electrode during the charging process, and doping phenomenon occurs actively when an electrolyte containing lithium metal is used Lt; / RTI &gt;

9 is a graph showing charging / discharging efficiency and discharging capacity after pre-doping of an ultracapacitor manufactured according to Experimental Examples and Comparative Examples. 9 (a) is for an ultracapacitor manufactured according to an experimental example, and (b) is for an ultracapacitor manufactured according to a comparative example.

9, the discharging capacity of the ultracapacitor according to the embodiment is 17 F / g, the charging and discharging efficiency is 75%, the discharging capacity according to the comparative example is 14 F / g, and the charging and discharging efficiency is 54%. Discharge capacity and efficiency were higher than those of 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: metal cap
192: Gasket

Claims (9)

Preparing a positive electrode having a structure in which a positive electrode material containing activated carbon as a positive electrode active material is applied to one surface or both surfaces of a current collector having a plurality of holes passing through the top and bottom surfaces;
A negative electrode having a structure in which a negative electrode material including graphite is applied to one surface or both surfaces of a current collector having a plurality of holes passing through the top and bottom surfaces of the negative electrode active material;
Preparing an electrolyte solution in which a lithium salt and a lithium metal are dissolved in a non-aqueous solvent;
A separator disposed between the positive electrode and the negative electrode and between the positive electrode and the negative electrode to prevent a short circuit between the positive electrode and the negative electrode is disposed in the metal cap and the electrolyte is injected so as to impregnate the positive electrode and the negative electrode, Fabricating an ultracapacitor; And
And applying a voltage to the metal cap to perform a first charging process,
The positive electrode active material and the negative electrode active material have a weight ratio of 2.5: 1,
The current collector used for manufacturing the positive electrode and the current collector used for manufacturing the negative electrode are made of different metals,
The production of the positive electrode may be carried out,
A positive electrode material is prepared by mixing active carbon powder as a positive electrode active material, a conductive material, a binder and a dispersion medium, coating the positive electrode material on one side or both sides of the current collector, or pushing the positive electrode material into a sheet state, And then attaching or pressing to one side or both sides thereof,
2 to 20 parts by weight of the conductive material, 100 to 2 parts by weight of the activated carbon powder, 2 to 10 parts by weight of the binder, 100 to 3,000 parts by weight of the active carbon powder, By weight,
The production of the negative electrode,
A negative electrode material is prepared by mixing a graphite powder, a conductive material, a binder and a dispersion medium, which is a negative electrode active material, coating the negative electrode material on one side or both sides of the current collector, or pushing the negative electrode material into a sheet state, And then attaching or pressing to one side or both sides thereof,
Wherein the negative electrode material comprises graphite powder and 2 to 20 parts by weight of a conductive material per 100 parts by weight of graphite powder, 2 to 10 parts by weight of a binder with respect to 100 parts by weight of graphite powder, By weight,
The graphite powder includes at least one selected from natural graphite, artificial graphite and soft carbon graphite,
The activated carbon powder has a specific surface area of 1,000 to 3,000 m 2 / g,
The average particle size of the activated carbon powder is 0.5 to 20 占 퐉,
The average particle size of the graphite powder is 0.5 to 20 탆,
0.01 to 15.0 g of the lithium metal is dissolved in 10 ml of the non-aqueous solvent in which the lithium salt is dissolved,
Wherein lithium ions from the lithium metal and the lithium salt are doped on the surface and inside of the graphite in the first charging process.
The method of claim 1, wherein the lithium salt is LiPF 6, LiBF 4, LiSbF 6 , LiAsF 6, LiClO 4, LiCF 3 SO 3, LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2 and LiAlO 4, and LiAlCl 4 ,
Wherein the lithium salt is dissolved in the non-aqueous solvent at a concentration of 0.1 to 5.0M.
delete The method of claim 1, wherein the non-aqueous solvent comprises acetonitrile.
delete delete delete delete The method of claim 1, wherein the ultracapacitor is a wound capacitor,
The step of fabricating the ultra-
Connecting a first lead wire to the negative electrode;
Connecting a second lead wire to the anode;
Forming a roll-shaped roll canceller by sequentially laminating and coiling the anode, the second separator for preventing short-circuiting between the anode and the cathode, and the cathode;
Inserting the roll revolver into the metal cap; And
And injecting the electrolyte solution in which the lithium salt and the lithium metal are dissolved so that the anode and the cathode of the revolver are impregnated into the metal cap.
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