WO2013115594A1 - Ensemble d'électrodes, procédé de fabrication de celui-ci et batterie secondaire l'utilisant - Google Patents

Ensemble d'électrodes, procédé de fabrication de celui-ci et batterie secondaire l'utilisant Download PDF

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WO2013115594A1
WO2013115594A1 PCT/KR2013/000828 KR2013000828W WO2013115594A1 WO 2013115594 A1 WO2013115594 A1 WO 2013115594A1 KR 2013000828 W KR2013000828 W KR 2013000828W WO 2013115594 A1 WO2013115594 A1 WO 2013115594A1
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electrode
unit
porous polymer
separator
cells
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PCT/KR2013/000828
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English (en)
Korean (ko)
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이병선
임현철
최원길
서인용
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주식회사 아모그린텍
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    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/54—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • 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
    • 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
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention is an electrode assembly that can improve the productivity and safety by forming and separating the separator consisting of a porous polymer web of ultra-fine fibers in one or both surfaces of the positive electrode or the negative electrode by using an electrospinning method, and the production thereof It relates to a method and a secondary battery using the same.
  • Lithium secondary batteries generate electrical energy by oxidation and reduction reactions when lithium ions are intercalated / deintercalated at the positive and negative electrodes.
  • a lithium secondary battery is prepared by using a material capable of reversibly intercalating / deintercalating lithium ions as an active material of a positive electrode and a negative electrode, and filling an organic electrolyte or a polymer electrolyte between the positive electrode and the negative electrode.
  • a lithium secondary battery is composed of an electrode assembly in which a negative electrode plate and a positive electrode plate are wound or stacked in a predetermined form with a separator (separation membrane) interposed therebetween, and a case in which the electrode assembly and the electrolyte solution are stored.
  • the basic function of the separator of the lithium secondary battery is to prevent the short circuit by separating the positive electrode and the negative electrode, and furthermore, it is important to suck the electrolyte required for the battery reaction and maintain high ion conductivity.
  • an additional function is required to prevent the movement of substances that inhibit battery reaction or to secure safety when an abnormality occurs.
  • Lithium ion secondary batteries with high energy density and large capacity, secondary batteries including lithium ion polymer batteries should have a relatively high operating temperature range, and the temperature increases when they are continuously used in high rate charge / discharge states. Separators are required to have higher heat resistance and thermal stability than those required by ordinary separators. In addition, it should have excellent battery characteristics such as high ion conductivity that can cope with rapid charging and discharging and low temperature.
  • the separator is located between the anode and the cathode of the battery to insulate it, maintains the electrolyte to provide a path for ion conduction, and when the temperature of the battery becomes too high, a part of the separator melts to block pores in order to block the current.
  • the separator When the temperature rises further and the separator melts, a large hole is formed, which causes a short circuit between the anode and the cathode. This temperature is called SHORT CIRCUIT TEMPERATURE. In general, the separator should have a low shutdown temperature and a higher short circuit temperature.
  • the electrode part when an abnormal heat generation of the battery occurs, the electrode part may be contracted at 150 ° C. or more, resulting in a short circuit. Therefore, it is very important to have both the closing function and the heat resistance for high energy density and large sized secondary battery. That is, a separator having excellent heat resistance, low thermal shrinkage, and excellent cycle performance according to high ion conductivity is required.
  • polyolefin-based microporous polymer membranes such as polypropylene and polyethylene or multiple membranes thereof are usually used.
  • the porous membrane layer is in the form of a sheet or a film, there is a drawback that the sheet-like separator shrinks together with the pore blocking of the porous membrane due to heat generation due to internal short circuit or overcharge. Therefore, when the sheet-like separator collapses due to the internal heat generation of the battery, the separator is reduced and the missing part is directly in contact with the positive electrode and the negative electrode, which leads to ignition, rupture, and explosion.
  • the porosity of the commonly used polyolefin separator is about 40% and the pore size is several tens of nm in size, so there is a limit in ion conductivity for a large capacity battery. .
  • Korean Patent Laid-Open Publication No. 2004-108525 proposes a film-type separator consisting of a composite membrane in which a polymer nanoweb is laminated by electrospinning on a polyolefin-based porous membrane as a strength support.
  • Korean Patent Laid-Open No. 2011-35847 proposes a separator in which inorganic particles are coated on a polyolefin-based porous membrane using a binder.
  • lithium dendrite In the film-like separator, full charge lithium dendrite is formed during overcharging. This is because the film is formed in the excitation space between the negative electrode and the film, and lithium ions that cannot enter the inside of the negative electrode accumulate on the surface of the negative electrode, that is, the excitable space between the negative electrode and the film, and precipitate as a lithium metal phase. When lithium is deposited on the entire surface, the deposited lithium dendrites may penetrate through the separator on the film to contact the positive electrode and the negative electrode, and at the same time, side reaction between lithium metal and the electrolyte proceeds, and the battery ignites due to heat generation and gas generation. There is a problem, exploding.
  • the film-like separator is a polyolefin-based film separator, in addition to the portion damaged by the initial heat generation during internal short circuit, the peripheral film is continuously contracted or melted, and the portion where the film separator burns out becomes wider. Can be generated. That is, when the temperature of the battery suddenly rises due to external heat transfer or the like, there is a problem that the temperature rise of the battery continues for a certain time and the breakage of the separator occurs even though the micropores of the separator are closed.
  • International Publication No. WO 2001/89022 relates to a lithium secondary battery comprising a superfine fibrous porous polymer separator and a method for manufacturing the same, wherein the porous polymer separator melts one or more polymers or dissolves one or more polymers in an organic solvent.
  • a method of forming a porous separator by injecting a molten polymer or a polymer solution obtained by the method into a barrel of an electrospinning machine, and then injecting the molten polymer or a polymer solution through a nozzle onto a substrate to form a porous separator It is.
  • the porous polymer membrane is prepared by the electrospinning of a polymer solution in which at least one polymer is dissolved in an organic solvent to a thickness of 50 ⁇ m, to form a porous polymer membrane between the negative electrode and the positive electrode to produce a lithium secondary battery It is inserted and integrated into lamination.
  • Korean Patent Laid-Open Publication No. 2008-13208 discloses a heat-resistant ultra-fine fibrous separator and a manufacturing method thereof, and a secondary battery using the same.
  • the heat-resistant ultra-fine fibrous separator is manufactured by an electrospinning method and has a melting point of 180 ° C. It consists of ultrafine fibers of a heat resistant polymer resin having no abnormalities or melting points, or ultrafine fibers of a polymer resin capable of swelling in an electrolyte solution together with ultrafine fibers of a heat resistant polymer resin.
  • Patent Publication No. 2008-13208 proposes to contain 1-95% by weight of an inorganic additive such as TiO 2 in order to improve mechanical properties, ion conductivity, and electrochemical properties in the separator.
  • the inorganic additive when the inorganic additive is contained in a large amount of spinning solution, there is a problem in that the spinning is impossible due to the dispersibility, and when it is spun together with the polymer material, the strength of the inorganic additive is lowered because it acts as an impurity in the spun fiber.
  • film separators made of polyolefin-based film separators such as those disclosed in Japanese Patent Application Laid-Open Nos. 2005-209570 and 2004-108525, or nanofiber webs disclosed in Korean Patent Application No. 2008-13208, are separated from electrodes.
  • the assembly productivity is low as the manufacture is made in a state inserted between the positive electrode and the negative electrode after being manufactured in a state.
  • Korean Patent Laid-Open No. 2007-114412 discloses a plurality of penetrations to facilitate the access of the electrolyte to the corresponding portion of the separation film surrounding the side of the electrode assembly. The technique which formed the sphere is proposed.
  • such a stack type or stack-fold type electrode assembly has a low adhesion between the electrode and the separator, resulting in a high interface resistance between the electrode and the separator, and a problem of precipitation of lithium dendrite in the excited space between the cathode and the film separator. Can be.
  • Korean Patent Laid-Open No. 2010-72532 proposes a technique for forming a heat shrink suppressing polymer layer by electrospinning a shutdown polymer layer and a polyethylene terephthalate (PET) layer on an electrode plate.
  • the Patent Publication No. 2010-72532 proposes to integrally form two or more kinds of separators by electrospinning two or more polymers having different characteristics on one side of the electrode plate, thereby forming the separator on the electrode plate.
  • No technique has been proposed for the continuous mass production of integrally formed electrode assemblies.
  • Korean Patent Laid-Open Publication No. 2000-53776 fixes a plurality of electrodes on a surface of a rotating rotor plate, and arranges at least one nozzle for injecting a polymer solution from the top, and applies the voltage to the nozzles.
  • a technique for forming a polymer film on the substrate has been proposed, a technique for inexpensively producing a plurality of continuous electrodes has not been presented.
  • An electrode assembly capable of continuously producing a plurality of unit electrode cells in an in-line manner in which separators formed on one surface or both surfaces of the plurality of unit electrode cells are sequentially formed, and then sequentially separating the unit electrode cells; There is provided a method of manufacturing the same and a secondary battery using the same.
  • Another object of the present invention is to continuously mold a plurality of unit electrode cells by punch-molding an electrode strip coated with a negative electrode or a positive electrode active material on one or both surfaces of a strip-type electrode current collector in a step-by-step manner using progressive equipment.
  • the present invention provides an electrode assembly, a method of manufacturing the same, and a secondary battery using the same.
  • Another object of the present invention is to form a cell assembly by simply stacking the negative electrode and the positive electrode and the positive electrode formed by the separator by integrally forming the cathode or the positive electrode or both sides of the negative electrode and the positive electrode by the electrospinning method, the assembly and mass production
  • the present invention provides an excellent electrode assembly, a method of manufacturing the same, and a secondary battery using the same.
  • Another object of the present invention is to electrodeposit the polymer film of the inorganic pores directly on the surface of the negative electrode to form a close contact with the surface of the negative electrode can be suppressed dendrite formation to improve the stability of the electrode assembly, its manufacturing method and the same It is to provide the used secondary battery
  • Another object of the present invention is to punch-molded so that the unit electrode cells are connected to each other, and by stacking the unit electrode cells in a Z-folding manner, an electrode assembly that can simplify the assembly process and improve productivity, and a method of using the same It is to provide a secondary battery.
  • the electrode assembly of the present invention comprises a separator formed on both or both of the positive electrode and the negative electrode and the positive electrode and the negative electrode to separate the positive electrode and the negative electrode, the separator is made of swelling in the electrolyte solution It comprises a first porous polymer film layer made of a polymer material capable of conducting electrolyte ions, and a porous polymer web layer made of ultra-fine fibers of a mixture of heat-resistant polymers or heat-resistant polymers and swellable polymers and inorganic particles.
  • One of the cathodes has a plurality of first unit electrode cells connected by a connecting bridge and zigzag folded by the connecting bridge, and the other one of the anode and the cathode has a plurality of second unit electrode cells separated from each other and a first unit electrode. It is characterized by being inserted between the cells and stacked.
  • a first step of forming an electrode strip by coating an electrode active material layer on at least one surface of a strip-shaped electrode current collector, and sequential first blanking while continuously transporting the electrode strip.
  • the second blanking is performed to separate a plurality of unit electrode cells from the electrode strip, and the connection bridges of the first unit electrode cells of the unit electrode cells remain connected, and the connection bridges of the second unit electrode cells
  • a fourth step of cutting the first unit electrode cells are folded in a zigzag by a connecting bridge, and a second unit electrode cell is inserted between the first unit electrode cells.
  • the electrode assembly of the present invention forms a plurality of unit electrode cells by punch-molding an electrode strip coated with a negative electrode or a positive electrode active material on one or both surfaces of a strip-type electrode current collector in a step-by-step manner. Subsequently, a separator made of a porous nanofiber web is continuously formed on one or both sides of the plurality of unit electrode cells, and the plurality of unit electrode cells are continuously connected in an in-line manner to sequentially separate the unit electrode cells. There is an advantage to produce.
  • the electrode assembly of the present invention a plurality of unit electrode cells by punching the electrode strip coated with the negative electrode or the positive electrode active material on one side or both sides of the strip-type electrode current collector in a step-by-step manner using progressive equipment It has the advantage of producing continuous.
  • the electrode assembly manufacturing method of the present invention by assembling the negative electrode or the positive electrode or the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive electrode and the positive
  • the electrode assembly manufacturing method of the present invention can suppress the formation of the dendrite by forming a polymer film of the inorganic pores directly on the surface of the negative electrode to be in close contact with the surface of the negative electrode has the advantage that can improve the stability.
  • FIG. 1 is a cross-sectional view showing an electrode assembly according to a first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view illustrating an electrode assembly according to a second exemplary embodiment of the present invention.
  • FIG 3 is a plan view showing an electrode assembly according to a first embodiment and a second embodiment of the present invention.
  • FIG. 4 is a plan view illustrating a first unit electrode cell of the present invention.
  • FIG. 5 is a plan view illustrating a second unit electrode cell of the present invention.
  • FIG. 6 is a cross-sectional view illustrating a stacked state of an electrode assembly according to a first embodiment of the present invention.
  • FIG. 7 is a cross-sectional view illustrating a stacked state of an electrode assembly according to a second exemplary embodiment of the present invention.
  • FIG. 8 is a process flowchart showing a method of manufacturing an electrode assembly according to the present invention.
  • FIG. 9 is a plan view of a manufacturing apparatus for explaining a unit electrode cell manufacturing process using a continuous blanking method according to the present invention.
  • FIG. 10 is a cross-sectional view of the manufacturing apparatus for explaining the unit electrode cell blanking process of FIG. 9.
  • FIG. 1 is a cross-sectional view showing an electrode assembly according to a first embodiment of the present invention
  • Figure 2 is a cross-sectional view showing an electrode assembly according to a second embodiment of the present invention
  • Figure 3 is a first and second embodiment of the present invention It is a top view which shows the electrode assembly which concerns on an example.
  • the electrode assembly 10 largely includes a cathode 1 and an anode 2.
  • the negative electrode 1 is disposed to face the positive electrode 2 and includes a pair of negative electrode active material layers 13a and 13b formed on both sides of the negative electrode current collector 11 to form a bicell.
  • the negative electrode 1 may include negative electrode active material layers 13a and 13b formed on one surface of the negative electrode current collector 11 to form a full cell.
  • the positive electrode 2 includes positive electrode active material layers 23a and 23b formed on both surfaces of the positive electrode current collector 21 to form a bicell.
  • the positive electrode 2 may include positive electrode active material layers 23a and 23b formed on one surface of the positive electrode current collector 21 to form a full cell.
  • the cathode active material layers 23a and 23b include a cathode active material capable of reversibly intercalating and deintercalating lithium ions.
  • Representative examples of the cathode active material include LiCoO 2 , LiNiO 2 , LiNiCoO 2 , and LiMnO 2. , LiMn 2 O 4 , V 2 O 5 , V 6 O 13 or LiNi 1- xy Co x M y O 2 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ x + y ⁇ 1, M is Al Lithium-transition metal oxides such as metals such as Sr, Mg, and La).
  • the negative electrode active material layers 13 and 13a include a negative electrode active material capable of intercalating and deintercalating lithium ions, and the negative electrode active material may be crystalline or amorphous carbon, carbon fiber, or carbon based carbon composite. It may be selected from the group consisting of a negative electrode active material, tin oxide, lithiated thereof, lithium, lithium alloys and mixtures thereof. However, the present invention is not limited to the type of the negative electrode active material.
  • the negative electrode 1 and the positive electrode 2 are prepared by mixing an appropriate amount of an active material, a conductive agent, a binder, and an organic solvent to prepare a slurry, and then, as the negative electrode and the positive electrode current collectors 11 and 21, on both sides of a copper or aluminum sheet or the like. It can be obtained by casting the prepared slurry, drying and rolling.
  • the positive electrode is used by casting a slurry composed of LiCoO 2 , super-P carbon, PVdF as an active material, a conductive agent, a binder on an aluminum foil, and the negative electrode as MCMB (mesocarbon microbeads), super-P carbon, PVdF
  • MCMB mesocarbon microbeads
  • the positive electrode and the negative electrode after the slurry is cast, it is preferable to perform roll pressing in order to increase the adhesion between the particles and the metal foil.
  • Separation membranes 3a and 3b having a multi-layer structure on the surface of the negative electrode 1 are formed of a polymer that swells in an electrolyte solution to cover the negative electrode active material layers 13a and 13b, respectively, and is made of a polymer capable of conducting electrolyte ions.
  • the separators 3a and 3b may be porous polymer webs obtained by electrospinning swellable polymers instead of the first inorganic porous polymer film layers 31a and 31b.
  • the porous polymer web may be formed by dissolving a swellable polymer in a solvent to form a spinning solution, and then electrospinning the spinning solution on a negative electrode active material layer to form a porous polymer web made of ultra-fine fibers.
  • PVDF is obtained by calendering the porous polymer web at a temperature lower than the melting point of PVDF).
  • the first inorganic porous polymer film layers 31a and 31b formed to cover the negative electrode active material layers 13a and 13b in the negative electrode 1 are swelled in the electrolyte and polymers capable of conducting electrolyte ions, for example, Polyvinylidene fluoride (PVDF), Poly-Ethylen Oxide (PEO), polymethyl methacrylate (PMMA), or Thermoplastic Poly Urethane (TPU) can be used.
  • the first inorganic porous polymer film layers 31a and 31b form a spinning solution by dissolving the polymer in a solvent, and then electrospinning the spinning solution on the anode active material layer to form a porous polymer web made of ultra-fine fibrous fibers. By heat-treating or calendering the porous polymer web at a temperature lower than the melting point of the polymer, the polymer film layers 31a and 31b of the inorganic pores are obtained.
  • the heat treatment temperature may be performed at a temperature slightly lower than the melting point of the polymer because the solvent remains in the polymer web, and also to form the inorganic porous film while preventing the polymer web from completely melting by the heat treatment. to be.
  • the inorganic porous polymer film layers 31a and 31b made of a material capable of conducting electrolyte swelling and swelling in the electrolyte are directly electrospun onto the surfaces of the negative electrode active material layers 13a and 13b, respectively.
  • swelling is performed by the electrolyte solution while maintaining conduction of lithium ions while blocking the formation of space between the negative electrode active material layers 13a and 13b and the film to prevent lithium ions from accumulating and depositing into lithium metal. can do.
  • dendrite formation can be suppressed on the surface of the cathode 1 and safety can be improved.
  • the inorganic-containing porous polymer web layers 33a and 33b formed on the first inorganic porous film layers 31a and 31b dissolve a mixture of a heat resistant polymer or a heat resistant polymer and a swellable polymer and inorganic particles in a solvent to form a spinning solution. Thereafter, the spinning solution is electrospun on the first non-porous polymer film layers 31a and 31b to form a porous polymer web made of ultra-fine fibrous, and the obtained porous polymer web is formed by calendering at a temperature below the melting point of the polymer. .
  • the inorganic particles are Al 2 O 3 , TiO 2 , BaTiO 3 , Li 2 O, LiF, LiOH, Li 3 N, BaO, Na 2 O, Li 2 CO 3 , CaCO 3 , LiAlO 2 , SiO 2 , SiO, SnO, SnO 2 , PbO 2 , ZnO, P 2 O 5 , CuO, MoO, V 2 O 5 , B 2 O 3 , Si 3 N 4 , CeO 2 , Mn 3 O 4 , Sn 2 P 2 O 7 , Sn 2 B 2 O 5 , Sn 2 BPO 6 And at least 1 sort (s) selected from each mixture thereof can be used.
  • the content of the inorganic particles is preferably contained in the range of 10 to 25% by weight based on the total mixture when the size of the inorganic particles is between 10 and 100 nm. . More preferably, the inorganic particles are contained in the range of 10 to 20% by weight, and the size is in the range of 15 to 25 nm.
  • the heat resistant polymer and the swellable polymer are preferably mixed in a weight ratio of 5: 5 to 7: 3, and more preferably 6: 4.
  • the swellable polymer is added as a binder to help bond between the fibers.
  • the mixing ratio of the heat resistant polymer and the swellable polymer is less than 5: 5 by weight, the heat resistance is poor, and thus the high temperature characteristics are not obtained.
  • the mixing ratio is greater than 7: 3 by weight, the strength is decreased and radiation trouble occurs.
  • the heat resistant polymer resin usable in the present invention is a resin that can be dissolved in an organic solvent for electrospinning and has a melting point of 180 ° C. or higher, for example, polyacrylonitrile (PAN), polyamide, polyimide, polyamideimide, Aromatic polyesters such as poly (meth-phenylene isophthalamide), polysulfones, polyetherketones, polyethylene terephthalates, polytrimethylene terephthalates, polyethylene naphthalates, and the like, polytetrafluoroethylene, polydiphenoxyphosphazenes Polyphosphazenes such as poly ⁇ bis [2- (2-methoxyethoxy) phosphazene], polyurethane copolymers including polyurethanes and polyetherurethanes, cellulose acetates, cellulose acetate butyrates, cellulose acetate pros Cypionate and the like can be used.
  • PAN polyacrylonitrile
  • Polyamide polyimide
  • the swellable polymer resin usable in the present invention is a resin that swells in an electrolyte and can be formed into ultrafine fibers by electrospinning.
  • PVDF polyvinylidene fluoride
  • poly (vinylidene fluoride-co-hexa) Fluoropropylene) perfuluropolymer
  • poly (oxymethylene-oligo- Oxyethylene) polyoxides including polyethylene oxide and polypropylene oxide
  • polyvinylacetate poly (vinylpyrrolidone-vinylacetate)
  • polystyrene and polystyrene acrylonitrile copolymers polyacrylonitrile methyl methacrylate copolymers
  • Polyacrylic containing Casting reel can be given to the copolymer, polymethyl me
  • the separators 3a and 3b having a multi-layer structure are formed on the surface of the cathode 1.
  • the separators 3a and 3b may be formed on the surface of the anode 2 instead of the cathode 1.
  • the inorganic-containing porous polymer web layers 33: 33a and 33b are first formed on the surface of the anode 2, and the first inorganic porous polymer film layers 31: 31a and 31b are formed of the porous polymer web layer 33. It is formed on the surfaces of 33a and 33b to be in close contact with the cathode 1 during assembly.
  • the two-layer structure separation membranes 3a and 3b are formed on either the negative electrode 1 or the positive electrode 2, but the separation membrane 3 is the first as shown in the second embodiment shown in FIG. It is composed of the inorganic porous polymer film layers 31: 31a and 31b and the inorganic-containing porous polymer web layers 33: 33a and 33b, and may be formed separately from the cathode 1 and the anode 2.
  • the first non-porous polymer film layers 31: 31a and 31b are formed on the negative electrode 1 to cover the negative electrode active material layers 13a and 13b, and the inorganic material to cover the positive electrode active material layers 23a and 23b. It is also possible that the porous polymeric web layers 33: 33a and 33b are formed on the anode 2.
  • the second inorganic porous polymer film layer on the surfaces of the inorganic material-containing porous polymeric web layers 33a and 33b of the anode 2 in the same manner as the first inorganic porous polymer film layers 31a and 31b.
  • the first inorganic porous polymer film layers 31a and 31b and the second inorganic porous polymer film layer are bonded to each other.
  • the first inorganic porous polymer film layers 31a and 31b and the inorganic material-containing porous polymer web layers 33a and 33b may be integrally formed on the negative electrode 2 or may be formed separately from the negative electrode 1 and the positive electrode 2.
  • the thickness of the inorganic-containing porous polymer web layer (33a, 33b) is set in the range of 5 to 50um
  • the thickness of the first inorganic porous polymer film layer (31a, 31b) is preferably set in the range of 5 to 14um.
  • the function of the separator is that the inorganic-containing porous polymer web layers 33a and 33b have a higher porosity than the first inorganic-porous polymer film layers 31a and 31b, and thus the first inorganic rather than the inorganic-containing porous polymer web layers 33a and 33b.
  • the thickness of the first inorganic porous polymer film layers 31a and 31b is preferably adjusted in consideration of the ion conductivity and energy density of the film layer.
  • the first inorganic porous polymer film layers 31a and 31b and the inorganic porous polymer web layers 33a and 33b serving as separators may be formed of the cathode 1 or the anode 2 as shown in FIG. 1. It encloses with a sealing structure, or surrounds the cathode 1 and the anode 2 simultaneously with the sealing structure like FIG.
  • the electrode assemblies 10 and 10a of the present invention may form a unit cell by simply stacking the cathode 1 and the anode 2, for example, a large capacity for an electric vehicle.
  • the present invention has a high assembly productivity compared to the prior art that goes through the process of folding a plurality of bi-cell with a separate membrane film.
  • the negative electrode 1 and the positive electrode 2 are provided with the negative electrode and positive electrode terminals 11a and 21a which protrude a part of the negative electrode and the positive electrode current collectors 11 and 21.
  • the electrode assemblies 10 and 10a of the present invention are laminated and assembled with a plurality of negative electrodes 1 and positive electrodes 2, the negative electrode terminal 11a of the negative electrode 1 and the positive electrode terminal 21a of the positive electrode 2 as shown in FIG. 3. ) Are stacked so that they face in opposite directions.
  • porous polymer web layers 33a and 33b contain an inorganic material and thus retain their shape without shrinking or melting even when heat-treated at 500 ° C.
  • the electrode of the present invention maintains a constant voltage between 5V and 6V and a battery temperature of less than 100 ° C by continuously consuming overcharge current by causing a very small short-circuit rather than a hard short during overcharge. Overcharge stability can also be improved.
  • the secondary battery of the present invention includes an electrolyte in an electrode assembly including a separator.
  • the electrolyte according to the present invention includes a non-aqueous organic solvent, and the non-aqueous organic solvent may be carbonate, ester, ether or ketone.
  • the present invention is not limited to the type of nonaqueous organic solvent.
  • the electrolyte according to the present invention includes a lithium salt
  • the lithium salt acts as a source of lithium ions in the battery to enable the operation of the basic lithium battery, for example 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 , LiAlO 4 , LiAlCl 4 , LiN (C x F 2x +1 SO 2 ) (C y F 2x +1 SO 2 ), wherein x and y are natural water and LiSO 3 CF 3 , including one or more or mixtures thereof.
  • FIG. 4 is a plan view of the first unit electrode cell in the unfolded state
  • FIG. 5 is a plan view of the second unit electrode cell in accordance with the present invention
  • FIG. 6 is an electrode assembly according to the first embodiment of the present invention.
  • 7 is a stacked cross-sectional view
  • FIG. 7 is a cross-sectional view of stacked electrode assemblies according to a second embodiment of the present invention.
  • the electrode assembly is manufactured by a method of manufacturing an electrode assembly, which will be described later.
  • a plurality of unit electrode cells are formed by blanking (ie, punching) while continuously transporting the cathode 1 and the anode 2 in a strip form.
  • 50 and 60 are formed, and separators are formed on both sides of the unit electrode cells 50 and 60.
  • the unit electrode cells 50 and 60 are manufactured to be separated from each other and the plurality of first unit electrode cells 50 connected by the connection bridge 24. It consists of a plurality of second unit electrode cells (60). The manufacturing method of such unit electrode cells 50 and 60 will be described in detail below.
  • the first unit electrode cells 50 are connected by a plurality of connection bridges 24, and the space between the connection bridges 24 is filled with a separator. Therefore, since the entire first unit electrode cell is covered with the separator, the sealing performance can be improved.
  • the first unit electrode cell 50 is Z-folded in a zigzag form by the connecting bridge 24, and the second unit electrode cell 60 is inserted between the first unit electrode cells 50 and alternately. Are stacked.
  • the electrode assembly 10 may have a structure as illustrated in FIG. 6.
  • the cathode 1 on which the separators 3a and 3b are formed becomes the first unit electrode cell 50, and the anode 2 without the separator becomes the second unit electrode cell 60.
  • the anode 2 it is also possible for the anode 2 to be the first unit electrode cell 50 and the cathode 1 to be the second unit electrode cell 60.
  • the first unit electrode cell 50 according to the first embodiment is manufactured with the connection bridge 24 connected when the first unit electrode cell 50 is continuously manufactured, and thus, between the first unit electrode cells 50. Is continuously connected by the connecting bridge 24.
  • the manufactured first unit electrode cells 50 are folded in a zigzag form at regular intervals. Then, the plurality of first unit electrode cells 50 are connected to each other by the connecting bridge 24, and are folded and stacked in a zigzag manner, thereby easily stacking and improving productivity.
  • the second unit electrode cell 60 When the second unit electrode cell 60 is inserted between the first unit electrode cells 50 folded in a zigzag form, the first unit electrode cells 50 and the second unit electrode cells 60 are alternately stacked. . In this case, one of the second unit electrode cells 60 is inserted in front of the first unit electrode cell 50, and then the second unit electrode cell 60 is inserted behind the first unit electrode cell 50. do.
  • connection bridge 24 is laminated on the first extension part 56 on which the negative electrode current collector 11 of the first unit electrode cell 50 extends, on one side or both sides of the first extension part 56, and the separator 3a. 3b) is composed of second extension portions 52, 54 extending therefrom.
  • one of the anode unit electrode cells is inserted in the first unit electrode cell 50 in front of the cathode unit electrode cell, and the next anode unit electrode cell is inserted in the rear of the cathode unit electrode cell.
  • the anode unit electrode cells and the cathode unit electrode cells are alternately stacked alternately.
  • connection bridge 24 is laminated on the first extension part 56 on which the negative electrode current collector 11 of the first unit electrode cell 50 extends, on one side or both sides of the first extension part 56, and the separator 3a. 3b) is composed of second extension portions 52, 54 extending therefrom.
  • the connecting bridge 24 must be bent in order to be bent in order to stack the first unit electrode cells 50 in a zigzag. Therefore, the connecting bridge 24 is thinned by removing the negative electrode active material layers 13a and 13b in the unit electrode cell manufacturing process.
  • connection bridge 24 may be formed of only the negative electrode current collector 11 from which the separators 3a and 6b and the negative electrode active material layers 13a and 13b are removed.
  • the electrode assembly 10a illustrated in FIG. 2 When the electrode assembly 10a illustrated in FIG. 2 is stacked in a Z-folding manner, the electrode assembly 10a may have a structure as illustrated in FIG. 7.
  • the electrode assembly according to the second exemplary embodiment is connected to each other by a connecting bridge 24, and includes a plurality of first unit electrode cells 50 that are Z-folded in a zigzag form and separated from each other.
  • the second unit electrode cell 60 is inserted between the electrode cells 50.
  • the cathode 1 on which the separator 3 shown in FIG. 2 is formed becomes the first unit electrode cell 50
  • the anode 2 on which the separator 3 is formed becomes the second unit electrode cell.
  • the structure in which the anode 2 becomes the first unit electrode cell 50 and the cathode 1 becomes the second unit electrode cell 60 is also applicable.
  • connection bridge 24 may include a first extension part 62 in which the negative electrode current collector 11 of the first unit electrode cell 50 extends, and a separation layer stacked on one or both surfaces of the first extension part 62. It consists of the 2nd extension part 64 in which (3) extends.
  • the first unit electrode cell 50 is Z-folded in a zigzag form by a connecting bridge, and the second unit electrode cell 60 is interposed between the first unit electrode cells 50.
  • the first unit electrode cell 50 and the second unit electrode cell 60 are alternately stacked by inserting the first and second electrode cells 50.
  • the first unit electrode cell 50 and the second unit electrode cell 60 are alternately stacked to form the electrode assemblies 10 and 10a, and then placed in an aluminum or aluminum alloy can or similar container. Then, after closing the opening with a cap assembly, an electrolyte is injected to manufacture a lithium secondary battery.
  • FIG 8 is a process flowchart showing a manufacturing process of the unit electrode cell of the present invention
  • Figure 9 is a plan view showing a part of the manufacturing apparatus of the unit electrode cell of the present invention
  • Figure 10 is a manufacturing apparatus of the unit electrode cell of the present invention It is sectional drawing which shows a part.
  • both surfaces of the slurry including the negative electrode active materials 13a and 13b are cast and roll pressed so as to form a bicell on the negative electrode current collector 11 in the form of a strip to form a negative electrode strip 12 (S11). Use the winding on the reel. (S11)
  • the negative electrode active materials 13a and 13b formed in the negative electrode current collector 11 are formed with piercing holes 12a and 12b in a subsequent step, and also the negative electrode terminal 11a as shown in FIG. 9. It is desirable to exclude the constant width of both sides.
  • the pierce mold 16 is used to transfer the cathode strip 12 wound on the reel by step-by-step or continuously by using a pair of feed rollers 14a and 14b driven by a step motor or a servo motor.
  • a plurality of piercing holes (12a, 12b) are formed on both sides at regular intervals.
  • the plurality of piercing holes 12a and 12b may be used to determine the position of each electrode cell when the plurality of unit electrode cells continuously connected are separately separated in the secondary process.
  • the piercing holes 12a and 12b are generally holes used to transfer materials, the battery electrode material is thin and cannot be transferred using the piercing holes 12a and 12b, but is a strip material used as a current collector. It may be applied depending on the type or thickness of the.
  • masking tapes 15a and 15b are attached to the portion where the negative electrode terminal 11a is formed so as to omit the uncoated portion forming process, thereby forming a separator.
  • the pierce holes 12a and 12b may be used for the use of the negative electrode strip 12 as both sides of the negative electrode current collector 11 increase in tensile strength.
  • the feeding of the cathode strip 12 may be fed by motor rotation through the rollers 14a and 14b, and protrusions are formed on the rotating rollers by using the piercing holes 12a and 12b.
  • the piercing holes (12a, 12b) is fixed as a gear can be transported in accordance with the rotation of the rotary roller.
  • the piercing hole 12a is formed with a separator for the unit electrode cells 50 and 60 and the unit electrode cells 50 and 60 in a subsequent process, and then together with the negative electrode terminal 11a or the positive electrode terminal 21a.
  • the negative electrode At least two piercing holes 12a located outside the terminal 11a or the positive terminal 21a can be used when the negative electrode 1 and the positive electrode 2 are stacked.
  • blanking i.e., punching
  • the plurality of unit electrode cells 50 and 60 can be removed from the negative electrode strip 12.
  • the negative electrode strip 12 it is transferred by 1 unit process length, and blanking is performed for each unit process (1ST, 2ST), and between adjacent unit electrode cells (50, 60).
  • the unit electrodes cells 50 and 60 have a rectangular or square shape having a constant area. Punch to have shape.
  • the setting between the start part and the end part of the unit processes 1ST and 2ST can be modified differently.
  • the corners of the quadrangle are rounded so as to easily form a sealing structure when the separators are formed on both sides of the unit electrode cells 50 and 60 in a subsequent process.
  • the unit electrode cells 50 and 60 form a separator using, for example, an air electrospinning (AES) method in a subsequent process
  • the polymer spinning solution is applied at a high pressure through a plurality of spinning nozzles.
  • each of the spinning nozzles is placed in an environment in which air is sprayed.
  • the unit electrode cells 50 and 60 need to block the flow of the unit electrode cells 50 and 60 to maintain their position in a high air pressure environment and to perform the electrospinning of the polymer spinning solution to form a separator. have.
  • the separate electrode unit cells 50 and 60 are also separated along the collector of the electrospinning equipment and are continuously transported to be wound on the winder for subsequent processing. It is highly desirable in terms of productivity that they are interconnected together.
  • connection bridges 24 are interconnected between the upper, middle, and lower sides of the unit electrode cells 50 and 60 in consideration of these points, and the unit electrode cells 50 On the upper side or the lower side of the 60, punching molding is performed such that a portion forming the negative electrode terminal 11a is connected to the negative electrode strip 12.
  • the negative electrode active materials 13a and 13b coated on the connection bridge 24 are removed in a subsequent process.
  • the first non-porous polymer film layer 31a is formed to cover the negative electrode active material layer 13a.
  • the first non-porous polymer film layer 31a swells in an electrolyte and forms a spinning solution by dissolving a polymer capable of conducting electrolyte ions, for example, PVDF in a solvent, and forming the spinning solution in the negative electrode active material layer.
  • the electrospinning (13a) to form a porous polymer web made of ultra-fine fibrous the first non-porous polymer film layer 31a by heat-treating or calendering the porous polymer web at a temperature slightly lower than the melting point of the polymer To form.
  • the heat treatment temperature may be performed at a temperature slightly lower than the melting point of the polymer because the solvent remains in the polymer web, and the inorganic web film is formed while preventing the polymer web from completely melting by the heat treatment. For sake.
  • the radiation method applied to the present invention is a general electrospinning, air electrospinning (AES: Air-Electrospinning), electrospray (electrospray), electrobrown spinning (centrifugal electrospinning), flash Any one of flash-electrospinning can be used.
  • AES Air-Electrospinning
  • electrospray electrospray
  • electrobrown spinning electrobrown spinning
  • flash Any one of flash-electrospinning can be used.
  • the spinning solution is, for example, using a multi-hole spinning pack in which a plurality of spinning nozzles are disposed in the traveling direction and the perpendicular direction of the collector, air electrospinning in which air is sprayed for each spinning nozzle ( AES: It is preferable to use the air-electrospinning (AES) method.
  • AES air-electrospinning
  • the first non-porous polymer film layer 31 b is formed to cover the negative electrode active material layer 13 b by the same method as the method of forming the first non-porous polymer film layer 31 a.
  • an inorganic-containing porous polymer web layer 33a, 33b is formed on the first non-porous polymer film layers 31a and 31b, which is made of a ultrafine fibrous form of a mixture of a heat resistant polymer or a heat resistant polymer and a swellable polymer and inorganic particles.
  • the inorganic-containing porous polymer web layers 33a and 33b first dissolve a heat-resistant polymer or a mixture of a heat-resistant polymer and / or a swellable polymer and an inorganic particle in a solvent to form a spinning solution, and the spinning solution is a first inorganic polymer film.
  • Electrospinning, preferably air electrospinning, on the layer 31a forms a first porous polymeric web made of ultrafine fibrous form.
  • first and second porous polymer webs are calendered to obtain inorganic-containing porous polymer web layers 33a and 33b.
  • the method of forming the separation membranes 3a and 3b of the two-layer structure may be formed in a different order than the above method.
  • the first non-porous polymer film layer 31a and the inorganic-containing porous polymer web layer 33a are sequentially formed to cover the negative electrode active material layer 13a, and then cover the negative electrode active material layer 13b on the opposite side. It is also possible to sequentially form the first non-porous polymer film layer 31b and the inorganic-containing porous polymer web layer 33b.
  • the plurality of first unit electrode cells 50 for the cathode are secondly blanked by being connected to each other by the connecting bridge 24.
  • the first unit electrode cell 50 of is separated from the electrode strip.
  • the first unit electrode cells 50 are manufactured in a state of being connected to each other by the connection bridge 24.
  • the connecting bridge 24 includes only the separators 3a and 3b from which the negative electrode active materials 13a and 13b are removed and the negative electrode current collector 11, the connection bridge 24 can be bent relatively easily, thus zigzag the first unit electrode cells 50. It is relatively easy to fold when folding with.
  • the first unit electrode cell 50 is formed.
  • the structure in which the anode 2 is formed of the first unit electrode cell 50 and Z-folded and the cathode 1 is formed of the second unit electrode cell 60 is also applicable.
  • the first unit electrode cell 50 forming the negative electrode 1 may cover the negative electrode active material layer 13a.
  • the first non-porous polymer film layer 31 a is formed, and then the first non-porous polymer film layer 31 b is formed to cover the negative electrode active material layer 13 b (S13).
  • a mixture of a heat resistant polymer or a heat resistant polymer and / or a swellable polymer and inorganic particles is dissolved in a solvent so as to cover the cathode active material layer 23a.
  • electrospinning the spinning solution to form the first porous polymer web and then spinning the same spinning solution to cover the positive electrode active material layer 23b to form a second porous polymer web.
  • the first and second porous polymer webs are calendered to form inorganic-containing porous polymer web layers 33a and 33b.
  • the first non-porous polymer film layers 31: 31a and 31b are formed in the first unit electrode cell 50 so as to cover the negative electrode active material layers 13a and 13b, and then both surfaces thereof have a single layer structure.
  • Cutting lines 40 are provided in the separator 3 region extending from the first unit electrode cell 50 while being transferred in a step-by-step manner to the plurality of first unit electrode cells 50 for the cathode surrounded by the separator 3. ), And punching molding to separate the negative electrode terminal 11a is performed (S14). At this time, the first unit electrode cells 50 are maintained by the connection bridge 24.
  • the first unit electrode cell 50 is folded in a zigzag by the connecting bridge 24,
  • the second unit electrode cell 60 is inserted between the one unit electrode cell 50 to alternately stack the first unit electrode cell and the second unit electrode cell (S15).
  • the electrode assemblies 10 and 10a which are pressed and assembled by opposing the positive electrode 2 and the negative electrode 1, are manufactured in a large size such as a large capacity battery for an electric vehicle, a plurality of unit electrode cells may be used. After simply stacking (S15), the case assembly process may proceed (S16).
  • the electrolyte is injected (S17) to manufacture a secondary battery.
  • the negative electrode 1 and / or the positive electrode 2 have a structure sealed by a separator, the negative electrode 1 and the positive electrode 2 are simply opposed to each other and pressed to assemble the electrode assembly 10. 10a), ie, a unit cell can be formed, and thus, it has a high assembly productivity compared to the prior art, which undergoes a process of folding a plurality of bi-cells into separate separator films.
  • the inorganic porous polymer film layers 31a and 31b made of a material capable of conducting electrolyte swelling with swelling in the electrolyte are formed in close contact with the surfaces of the negative electrode active material layers 13a and 13b. While swelling is performed, the formation of spaces between the negative electrode active material layers 13a and 13b and the film can be prevented while the conduction of lithium ions is maintained, thereby preventing lithium ions from accumulating and depositing into lithium metal. As a result, the negative electrode 1 Dendrite formation can be suppressed on the surface), and safety can be improved.
  • the present invention can improve the productivity of the electrode assembly used in the secondary battery, thereby reducing the price of the secondary battery, it can be applied to various fields such as electric vehicles and electronic devices using the secondary battery.

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Abstract

L'ensemble d'électrodes de la présente invention comprend : une cathode ; une anode ; et une couche de séparation formée sur la cathode ou l'anode, ou sur les deux, de manière à séparer la cathode de l'anode. La couche de séparation comprend : une première couche de film polymère non poreux constituée d'un matériau polymère qui gonfle dans un électrolyte et peut conduire les ions de l'électrolyte ; et une couche de bande polymère poreuse, de structure micro-fibreuse, qui est constituée d'un polymère résistant à la chaleur ou d'un mélange d'un polymère résistant à la chaleur, d'un polymère gonflant, et de particules inorganiques. Une entité parmi la cathode et l'anode comprend une pluralité de cellules d'électrode de première unité qui sont connectées l'une à l'autre par des ponts de connexion et qui sont pliées en zigzag au moyen des ponts, et l'autre parmi la cathode et l'anode comprend une pluralité de cellules d'électrode de seconde unité, qui sont séparées l'une de l'autre et sont insérées entre les cellules d'électrode de première unité. Ainsi, le processus d'assemblage peut être simplifié et la productivité améliorée.
PCT/KR2013/000828 2012-02-02 2013-02-01 Ensemble d'électrodes, procédé de fabrication de celui-ci et batterie secondaire l'utilisant WO2013115594A1 (fr)

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