WO2001057942A1 - Battery and method of manufacture thereof - Google Patents
Battery and method of manufacture thereof Download PDFInfo
- Publication number
- WO2001057942A1 WO2001057942A1 PCT/JP2000/000607 JP0000607W WO0157942A1 WO 2001057942 A1 WO2001057942 A1 WO 2001057942A1 JP 0000607 W JP0000607 W JP 0000607W WO 0157942 A1 WO0157942 A1 WO 0157942A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrolyte
- battery
- power generation
- generation element
- electrolytic solution
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
- H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a method for manufacturing a battery. More specifically, the present invention relates to a method for manufacturing a lithium secondary battery. Background technology
- Lithium-ion rechargeable batteries are currently being actively improved as rechargeable batteries capable of realizing high voltage and high working energy density. Its main components are a pair of positive and negative electrodes and a power generating element consisting of a pair of electrodes separated from each other so as not to short-circuit between the two electrodes. The body and the electrolyte filled in the power generation element body. Lithium rechargeable batteries that are in practical use are inserted into an outer can with the positive and negative electrodes and separators wrapped around each other and sealed after filling with electrolyte. Manufactured by mouth-to-mouth procedures. An example of such a manufacturing method can be found in Japanese Patent Application Laid-Open No. 10-333488, for example.
- the amount of electrolyte required for a lithium ion battery is ideally enough to fill both the positive and negative electrodes, which are porous materials, and the voids in the separator. .
- a battery such as a gap between an outer can and an electrode or a gap in a winding center formed when an electrode is overlapped and wound.
- the space filled with the electrolyte is irrelevant to this function. Due to the presence of the electrolyte in the space irrelevant to the battery function, the amount of the electrolyte is much larger than the ideally required amount, and the weight increase is necessary.
- the electrolyte present in the space irrelevant to the battery function flows and flows out as compared with the electrolyte held in a porous body such as an electrode and a separator. It's easy to do . This can cause a battery fluid accident.
- the electrolyte present in the space unrelated to the battery function is less in terms of suppressing the leakage of the battery even in the heavy surface. I want to do that. Disclosure of the invention
- the present invention has been made to solve the above problems, and the amount of the electrolyte present in the space irrelevant to the above-mentioned battery function is extremely large.
- the aim is to produce a small number of batteries.
- the present inventors have conducted research on a battery manufacturing method for the purpose of obtaining a small, lightweight and high-performance battery, and have found that the battery manufacturing method, the battery manufacturing apparatus, and the battery described below are used. Completed.
- the present invention is a.
- a part of the electrolyte adhering to the electricity-generating element body filled with the electrolyte is a liquid in which the amount of dissolved solids is less than that of the electrolyte and is compatible with the electrolyte.
- the method for producing a battery described in Claim 1 having a step of diluting with a battery (Claim 9 of the claim), the amount of solid dissolved more than the electrolytic solution is defined as the electrolytic solution.
- the method for producing a battery according to Claim 9, wherein the liquid having a low level of compatibility and being compatible with the electrolyte is a solvent constituting the electrolyte. 10 terms)
- FIG. 1 shows the power generation element according to one embodiment of the present invention, which is attached to the power generation element by irradiating the airflow ejected from the nozzle onto the power generation element.
- FIG. 2 is a schematic view showing an outline of a step of removing a part of the electrolyte solution.
- FIG. 2 shows a nozzle having a slit-shaped outlet for generating a band-shaped airflow corresponding to a power generating element according to an embodiment of the present invention.
- FIG. 2 is a schematic view showing an outline of the shape.
- FIG. 3 shows a nozzle having a series of holes in the form of holes that generate a band-shaped airflow that strikes the power generating element according to an embodiment of the present invention.
- FIG. 2 is a schematic view showing an outline of the above.
- FIG. 4 shows an example of the embodiment of the present invention, in which one of the flow paths into which the power generating element is inserted is depressurized to create an airflow, thereby adhering to the power generating element.
- FIG. 4 is a schematic view showing an outline of a process for removing a part of the electrolyte solution thus obtained.
- 1 indicates a power generating element
- 2 indicates a nozzle for ejecting gas
- 3 indicates an air flow.
- reference numeral 2 denotes a nozzle for ejecting gas
- reference numeral 3 denotes an air flow
- reference numeral 2 denotes a nozzle for ejecting gas
- reference numeral 3 denotes an air flow
- 1 indicates a power generating element
- 3 indicates an air flow
- 4 indicates a gas flow path. Best form to carry out the invention
- the battery manufacturing method of the present invention comprises the following steps: (i) charging the electrolyte into the power generating element in which the positive electrode, the negative electrode, and the separator are integrated; Removing part of the electrolytic solution adhering to the generated power element, and (iii) cleaning the power element from which a part of the adhering electrolytic solution has been removed. It has a process of storing it in an outer container. The details of the content are described below.
- the power generation element of the battery is a combination of the positive electrode, the negative electrode, and the separator-electrode.
- the positive sheet and the negative sheet And the separator file that separates them from each other.
- lithium conodate powder is bound on aluminum foil using polyvinylidene fluoride as a binder. Coated and dried products can be used.
- polyvinylidene fluoride is used as a binder, and graphite carbon powder is applied to a copper foil and dried. You can use the dried one.
- a porous polylene film can be used as a separator.
- an electrolytic solution When an electrolytic solution is filled in a power generating element having a self-supporting structure, it becomes a state of functioning as a battery.
- an electrolytic solution obtained by dissolving various kinds of electrolytes in an arbitrary solvent can be used.
- a solvent for the electrolytic solution for example, ethylene carbonate and dimethyl carbonate are used. Mixed solvents can be used.
- the electrolyte for example, lithium hexafluoride can be used.
- the electrolyte can be filled outside the battery outer container. If the power generation element is relatively large or the electrode has a dense layer, impregnate and fill the electrolyte with high efficiency up to the innermost part of the power generation element. Is difficult. If the pressure is reduced or centrifugal force is applied while the entire power generating element is submerged in the electrolyte, the electrolyte is impregnated with a high efficiency and a high filling rate to fill the electrolyte. Can be done.
- the degree of decompression can be, for example, slightly higher than the pressure at which the electrolyte undergoes reduced pressure boiling.
- the centripetal force can be, for example, about four times the rotational speed and gravity that generates 4G.
- the amount of the surplus electrolyte existing in the space irrelevant to the battery function is reduced. It can be reduced.
- the power generating element By placing the power generating element in the airflow, it is possible to remove a part of the electrolyte adhering to the power generating element.
- the gas that creates the airflow is, for example, dry air. , Dry nitrogen can be used. Dry air and dry nitrogen do not adversely affect battery performance.
- a method for removing excess electrolyte is to blow high-speed airflow. There is a way to attach it. A part of the electrolyte adhering to the power generation element can be removed by irradiating the air flow ejected from the nozzle onto the power generation element.
- Fig. 1 shows the outline of the process of removing a part of the electrolyte adhering to the power generation element by applying the airflow blasted from nozzle nozzles to the power generation element. Indicate Blowing the airflow from the nozzle onto the surface of the power-generating element causes the attached electrolyte to be removed by the pressure.
- the part that removes the electrolyte is moved strongly, that is, the part where the airflow is directly applied is moved (Scanning)-it is possible to remove excess electrolyte efficiently over the entire power generation element body.
- the part to which the airflow is directly applied is scanned by moving the power generating element or the nozzle. You can do it.
- the scanning speed can be, for example, about 5 cm per second.
- the air flow ejected from the nozzle is in a range of 30 to 90 ° with respect to a normal of a surface of the power generating element body from which liquid is removed. If the angle is less than 30 °, the blown droplets are not scattered in one direction and the possibility of contaminating the already removed surface is increased.
- Nozzles are shaped like a strip-shaped ejected rocker with a band-like airflow, and a band-shaped nozzle from a row of hole-shaped outlets. Those that generate airflow are preferred.
- Figure 2 shows an outline of a nozzle with a slit-shaped outlet.
- Figure 3 shows an outline of a nozzle with a series of holes.
- the velocity of the airflow ejected from the nozzle can be about 40 m / s. Intention to erupt from the nozzle If the flow speed is too slow, there is a tendency that it is difficult to sufficiently remove the excess electrolyte. If the flow speed is too fast, the power generation element will lose airflow. It may be deformed by the pressure.
- a method for removing excess electrolyte there is a method in which a power generating element is placed in a flow path, and a high-speed airflow is caused to flow through the flow path.
- the flow velocity of the airflow flowing through the channel can be, for example, about 20 m / sec. If the flow velocity is too high, the power generating element tends to deform, and if the flow velocity is too low, it is difficult to remove excess electrolyte sufficiently. Tend .
- Gas can be created by sending gas from one of the channels into which the power generating element is inserted, or by depressurizing one of the channels.
- Fig. 4 shows the outline of the process of removing a part of the electrolyte adhering to the power generation element body by reducing the pressure in one of the flow paths in which the power generation element body is inserted and creating an air flow. .
- a method of removing excess electrolyte there is a method of contacting with an object having a function of absorbing the electrolyte.
- an object having a function of absorbing and retaining an electrolytic solution for example, a nonwoven fabric, a woven fabric, a sponge-like resin or the like that absorbs the liquid material may be used. I can do it.
- the battery can be formed.
- the external container for example, use a metal can or aluminum laminate file made of stainless steel. can do .
- the weight of the battery can be reduced, and the possibility of liquid leakage can be significantly reduced.
- the step of removing excess electrolyte, depending on the type of electrolyte solids in the electrolyte are remarkably deposited on the surface of the power generating element due to evaporation of the solvent depending on the type of the electrolyte. May be issued.
- concaves and convexes may appear on the surface of the external container, resulting in an unfavorable appearance. .
- a part of the electrolyte adhering to the power generating element body is dissolved in a smaller solid component than the electrolyte.
- Dilution with a liquid (washing solution) that is compatible with the constituents of the electrolytic solution can reduce the precipitation of solid components.
- a part of the electrolytic solution attached to the power generation element body can be diluted by rinsing the power generation element body with the cleaning liquid.
- a washing liquid a liquid in which solid components are not dissolved or a liquid with a small amount of dissolution, for example, a solid component in which the solid components are dissolved less than the electrolytic solution is smaller.
- Liquids can be used, and liquids that have little effect on battery performance and liquids that are compatible with the electrolyte can be used.
- a solvent obtained by removing solutes such as salts from the constituent components of the electrolyte solution should be used favorably because it does not affect battery performance.
- the cleaning liquid include, but are not limited to, ethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, and the like. You can use bottles, cubractons, and so on.
- the amount of electrolyte that does not contribute to the function of the battery is reduced, so that the battery is lightweight and hard to leak. Batteries that do not have problems with their performance or appearance can be manufactured.
- the battery manufacturing apparatus comprises: (i) a step of filling a positive electrode, a negative electrode, and a power generating element united with a cell and a battery with an electrolyte; Means for removing part of the electrolytic solution adhering to the power generating element, and (iii) storing the power generating element from which the part of the adhering electrolytic liquid has been removed in an outer container.
- the means for filling the power generating element body with the electrolytic solution has, for example, an electrolytic solution tank for immersing the power generating element body in the electrolytic solution.
- Means for removing a part of the electrolyte adhering to the power generating element include, for example, a nozzle that blows out an air current, a flow path, and a blower that creates an air flow. Or a pressure reducing device or an object having a function of absorbing an electrolyte.
- the active material Meso-Fu-Zumicrobi-Zukabon (manufactured by Osaka Gas Co., Ltd.) is 95% by weight.
- a negative electrode active material paste prepared by mixing 5% by weight of vinylidene fluoride and NMP as a solvent is a collector made of a 12-m-thick copper foil. Thickness 2 according to doctor blade method
- the negative electrode material was prepared by coating and drying the solution to a thickness of 100 m and then rolling it to a thickness of 120 m.
- the cathode and anode materials prepared as described above were used for 50 mm
- the power generating element was put into the electrolyte, the whole was depressurized with a pump, kept at 50 t0 rr for 3 minutes, and then returned to normal pressure.
- the electrolyte is generated by a jet of dry air at a rate of 1 liter per second converted to normal pressure from a slit-shaped nozzle with a length of 70 mm and a width of 0.3 mm. Removal was performed. The angle at which the airflow is applied is assumed to be an inclination of 45 from the normal to the surface of the power generation element body. The distance from the end to the surface of the power generation element body was 5 mm. The removal was performed by scanning at a speed of 5 cm per second from one end of the power generating element body surface to the other end. The above operations were performed on both sides of the power generation element.
- the power-generating element body created in the above process was sealed with an aluminum film under a reduced pressure of about 50 torr to form an exterior.
- the aluminum film is an aluminum foil with a thickness of 50 / zm and a polystyrene telemeter with a thickness of 12 // m.
- a laminate of an irem and a 5 m thick polyethylene film was cut into 70 mm x 120 mm. This filem was folded in two to make it 70 mm X 60 mm, and the other three sides were sealed with a heat seal with the power generating element body sandwiched. .
- a hole with a diameter of 2 mm was drilled at the end of the exterior and held for 5 minutes with the hole down, and the amount of electrolyte flowing out was estimated from the weight change before and after.
- the weight of the battery prepared according to the above procedure was 13.5 g, and the amount of effluent from the liquid leakage evaluation was 0.05.
- Example 2 (when placed in a flow path)
- a cylindrical flow path was designed so that the gap between the inner wall of the flow path and the power generating element was 0.5 mm when the battery power generating element was inserted inside.
- the power generation element is fixed in this flow path, and excess air is removed by flowing dry air through the gap between the flow path and the power generation element. did .
- Power generation differential pressure of the upper stream side and the downstream side of the element body is 0. 5 kgf Roh cm 2 and dry air supply amount Adjusts to the jar by that Do not.
- a battery was prepared in the same manner as in Example 1 except that excess electrolyte was removed by the above-described method.
- the weight of this battery was 13.3 g, and the amount of effluent from the liquid leakage evaluation was 0.01 g.
- Example 3 (when non-woven fabric is used)
- Example 2 Same as Example 1 except that excess electrolyte is removed by wiping off the electrolyte adhering to the outside of the power generation element after injection with a non-woven polypropylene fabric.
- the battery was made like this.
- the weight of this battery was 13.6 g, and the amount of effluent by liquid leakage evaluation was 0.07 g. According to this method, a large amount of dry gas supply equipment is not required, but excess liquid in the center of the wound structure cannot be removed.
- Example 1 Immediately after immersing the power generating element body after filling the electrolyte in a JET CARBON for 10 seconds, a run to remove the excess electrolyte was performed. A battery was made in the same manner as in Example 1.
- the weight of this battery was 13.5 g, and the amount of effluent from the liquid leakage evaluation was 0.05 g. No minute solid deposits on the surface of the power generation element as observed in Example 1 were observed. No irregularities due to solid precipitates appeared on the surface even after the external mounting.
- the power generation element body is sandwiched between aluminum laminate films and sealed except one side to form a bag. Inside the bag-shaped external film The electrolyte solution was injected into the sample to perform vacuum impregnation of the electrolyte solution. The excess electrolyte solution after the impregnation was removed with a pipette, and the other side was sealed and sealed.
- Example 1 except for the above operations A battery was created in the same procedure as described above. The weight of this battery was 14.1 lg, and the amount of effluent from the liquid leakage evaluation was 0.9 g.
- the power generating element body is sandwiched between aluminum laminate films, sealed except for one side to form a bag, and the electrolytic film is placed inside the bag-shaped external film.
- the solution was injected to adjust the total weight of the battery to 13.5 g-. This weight is the same as in Example 1. After that, it was kept at 50 t0 rr for 3 minutes, and the other side was sealed and sealed.
- a battery was created in the same procedure as in Example 1 except for the above operation.
- the weight of this battery was 13.5 g, and the amount of effluent from the liquid leakage evaluation was 0.07 g.
- the discharge capacity was about 80% as compared with Example 1. It was.
- a battery was prepared in the same manner as in Example 1 except that the air flow at the time of removing the excess electrolyte was set to 0.2 liter per second. Even after the operation of removing the excess electrolyte, a noticeable electrolyte residue was observed on the surface of the power generation element body.
- the weight of this battery was 13.9 g, and the amount of effluent by liquid leakage evaluation was 0.5 g. In comparison, there was an increase in the amount of electrolyte due to excess electrolyte and an increase in the amount of electrolyte leading to liquid leakage, but it was remarkable when compared with Comparative Example 1 and Comparative Example 1. The effect was seen.
- a battery was prepared in the same manner as in Example 1 except that the air flow at the time of removing excess electrolyte was set to 2 liters per second.
- the amount of excess electrolyte which does not contribute to the battery function is small, so that the battery is lightweight and has a low possibility of liquid leakage. Can be manufactured.
- the battery according to claim 12 has a high weight energy density due to a decrease in the weight of the electrolyte, and an excess of the electrolyte is reduced. Therefore, the possibility of causing a liquid leakage accident is low.
- the battery manufacturing method, the battery manufacturing apparatus, and the battery according to the present invention include a lithium ion battery, such as a lithium ion battery, in a power generating element body impregnated with an electrolytic solution, and in an outer container for housing the power generating element body. It can be widely applied to batteries configured by this method.
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2000/000607 WO2001057942A1 (en) | 2000-02-04 | 2000-02-04 | Battery and method of manufacture thereof |
KR1020017012386A KR20020019008A (en) | 2000-02-04 | 2000-02-04 | Battery and method of manufacture thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/JP2000/000607 WO2001057942A1 (en) | 2000-02-04 | 2000-02-04 | Battery and method of manufacture thereof |
Publications (1)
Publication Number | Publication Date |
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WO2001057942A1 true WO2001057942A1 (en) | 2001-08-09 |
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Family Applications (1)
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PCT/JP2000/000607 WO2001057942A1 (en) | 2000-02-04 | 2000-02-04 | Battery and method of manufacture thereof |
Country Status (2)
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KR (1) | KR20020019008A (en) |
WO (1) | WO2001057942A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010109162A (en) * | 2008-10-30 | 2010-05-13 | Jcc Engineering Co Ltd | Method of manufacturing electrolytic capacitor, impregnation device for electrolytic capacitor, and machine for assembling electrolytic capacitor |
JP2016095987A (en) * | 2014-11-13 | 2016-05-26 | 株式会社豊田自動織機 | Method of manufacturing electrode and cleaning device of electrode |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011043608A2 (en) * | 2009-10-07 | 2011-04-14 | 주식회사 엘지화학 | Method for manufacturing a lithium ion polymer battery, battery cell, and lithium ion polymer cell comprising same |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02210769A (en) * | 1989-02-10 | 1990-08-22 | Seiko Electronic Components Ltd | Manufacture of nonaqueous battery |
JPH02262276A (en) * | 1989-03-31 | 1990-10-25 | Matsushita Electric Ind Co Ltd | Manufacture of nonaqueous electrolyte secondary battery |
JPH0714609A (en) * | 1993-06-21 | 1995-01-17 | Haibaru:Kk | Battery |
JPH10223255A (en) * | 1997-02-04 | 1998-08-21 | Toshiba Battery Co Ltd | Manufacture of polymer electrolyte secondary battery |
JPH10334926A (en) * | 1997-06-03 | 1998-12-18 | Toshiba Corp | Battery manufacturing device and manufacture |
JP2000123860A (en) * | 1998-10-13 | 2000-04-28 | Ngk Insulators Ltd | Electrolyte filling method of lithium secondary battery and electrode terminal structure |
-
2000
- 2000-02-04 WO PCT/JP2000/000607 patent/WO2001057942A1/en not_active Application Discontinuation
- 2000-02-04 KR KR1020017012386A patent/KR20020019008A/en not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02210769A (en) * | 1989-02-10 | 1990-08-22 | Seiko Electronic Components Ltd | Manufacture of nonaqueous battery |
JPH02262276A (en) * | 1989-03-31 | 1990-10-25 | Matsushita Electric Ind Co Ltd | Manufacture of nonaqueous electrolyte secondary battery |
JPH0714609A (en) * | 1993-06-21 | 1995-01-17 | Haibaru:Kk | Battery |
JPH10223255A (en) * | 1997-02-04 | 1998-08-21 | Toshiba Battery Co Ltd | Manufacture of polymer electrolyte secondary battery |
JPH10334926A (en) * | 1997-06-03 | 1998-12-18 | Toshiba Corp | Battery manufacturing device and manufacture |
JP2000123860A (en) * | 1998-10-13 | 2000-04-28 | Ngk Insulators Ltd | Electrolyte filling method of lithium secondary battery and electrode terminal structure |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010109162A (en) * | 2008-10-30 | 2010-05-13 | Jcc Engineering Co Ltd | Method of manufacturing electrolytic capacitor, impregnation device for electrolytic capacitor, and machine for assembling electrolytic capacitor |
JP2016095987A (en) * | 2014-11-13 | 2016-05-26 | 株式会社豊田自動織機 | Method of manufacturing electrode and cleaning device of electrode |
Also Published As
Publication number | Publication date |
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KR20020019008A (en) | 2002-03-09 |
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