WO2010116729A1 - リチウム二次電池用セパレータ、およびそれを用いたリチウム二次電池 - Google Patents
リチウム二次電池用セパレータ、およびそれを用いたリチウム二次電池 Download PDFInfo
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- WO2010116729A1 WO2010116729A1 PCT/JP2010/002519 JP2010002519W WO2010116729A1 WO 2010116729 A1 WO2010116729 A1 WO 2010116729A1 JP 2010002519 W JP2010002519 W JP 2010002519W WO 2010116729 A1 WO2010116729 A1 WO 2010116729A1
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M50/40—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
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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
- H01M50/40—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
- H01M50/417—Polyolefins
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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
- H01M50/40—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
- H01M50/423—Polyamide resins
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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
- H01M50/40—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
- H01M50/426—Fluorocarbon polymers
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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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
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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
- H01M50/40—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
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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
- H01M50/40—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
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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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
- H01M50/40—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
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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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
- H01M50/40—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
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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
- H01M50/40—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
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- 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
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- 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
Definitions
- the present invention relates to a separator for a lithium secondary battery and a lithium secondary battery using the same. More specifically, the present invention relates to an improvement for facilitating the configuration of an electrode group of a lithium secondary battery.
- lithium secondary batteries that can be repeatedly charged and discharged and have a high energy density have been used as power sources for mobile devices such as notebook computers and mobile phones.
- the lithium secondary battery since the lithium secondary battery has a high energy density, if the lithium secondary battery is misused such as an external short circuit, the battery reaction may be abrupt and the battery temperature may increase. Therefore, the lithium secondary battery is provided with a safety mechanism such as a PTC (Positive Temperature Coefficient) element or an SU circuit (protection circuit).
- a separator disposed between the positive electrode and the negative electrode, which are power storage units, is also provided with a safety mechanism against an increase in battery temperature.
- a porous film containing polyolefin is used for the separator.
- a sheet-like positive electrode, a negative electrode, and a separator are wound in a spiral shape so that the positive electrode and the negative electrode are alternately stacked with the separator in between. Make it.
- a non-aqueous electrolyte is injected, and the opening of the battery case is sealed, thereby producing a lithium secondary battery.
- the electrode group is formed by winding the positive electrode and the negative electrode together with the separator while rotating the two cores with the end of the separator sandwiched between the two metal cores. Is done. Winding is performed with separators disposed between the positive electrode and the negative electrode and in the innermost layer. After the winding is completed, the space between the two cores is widened and the core is removed from the electrode group.
- the slipperiness of the separator with respect to the core is small, the core may not be removed from the electrode group, or the separator may be caught on the burr of the electrode and the separator may be damaged. For this reason, it is necessary to constantly monitor the extraction state of the core, resulting in an increase in manufacturing cost. If there is a hindrance to the winding core extraction process, the production line needs to be stopped and readjusted, resulting in a decrease in productivity.
- Patent Document 1 proposes to improve the slipperiness of the separator by embedding a part of the particles in a protruding state on the surface of the separator.
- Patent Document 2 proposes to use a porous film having an outer surface portion of polypropylene containing 50 ppm or more of calcium stearate as a separator.
- Patent Document 1 there is a possibility that a portion of the porous film where the spherical particles do not protrude comes into contact with the core. If the surface of the porous film and the core are in direct contact, it will be difficult to smoothly pull out the core. Moreover, since spherical particles are embedded in the porous film, the slipperiness is insufficient.
- a porous film is produced by extrusion molding.
- it is necessary to add a large amount of particles in order to ensure a good release property by projecting a part of spherical particles from the surface.
- the film formability deteriorates.
- Patent Document 2 it is difficult to sufficiently improve the removability of the core in the battery only by adding calcium stearate. Furthermore, if the content of calcium stearate is increased, the film formability is reduced as described above.
- the present invention has been made in view of the above problems, and provides a separator for a lithium secondary battery capable of smoothly pulling out a core from a wound electrode group.
- One aspect of the present invention comprises a porous film including a polyolefin layer, and a lubricating layer including a particulate material disposed on the surface of the porous film, and the three-dimensional surface roughness of the lubricating layer is
- the present invention relates to a separator for a lithium secondary battery having a thickness of 0.15 to 1.45 ⁇ m.
- Another aspect of the present invention is a positive electrode, a negative electrode, and an electrode group including the separator interposed between the positive electrode and the negative electrode, a non-aqueous electrolyte, and a battery containing the electrode group and the non-aqueous electrolyte.
- the present invention relates to a lithium secondary battery including a case.
- the slipperiness of the separator with respect to the winding core can be remarkably improved.
- the removability of the core from the electrode group is improved, and the core can be smoothly pulled out.
- FIG. 1 is a schematic cross-sectional view of a lithium secondary battery according to an embodiment of the present invention. It is a top view which shows typically the arrangement
- FIG. 1 is a schematic cross-sectional view of a prismatic lithium secondary battery showing an example of an embodiment of the present invention.
- the battery 10 includes a thin box-shaped battery case 1, an electrode group 20 accommodated in the case 1, and a non-aqueous electrolyte (not shown).
- the electrode group 20 includes a rectangular flat surface and side surfaces having curved surfaces located at both ends of the flat surface.
- the electrode group 20 is configured by winding a long strip-shaped positive electrode 2 and a negative electrode 3 in a spiral shape with a long strip-shaped separator 4 interposed therebetween. At this time, the separator 4 is disposed on the innermost periphery of the electrode group 20. In the example of FIG. 1, the positive electrode 2, the negative electrode 3, and the separator 4 are wound so that the innermost separator 4 and the negative electrode 3 are in contact with each other.
- FIG. 2 is a top view for schematically explaining the configuration of the electrode group 20 using a winding core.
- two rectangular metal thin plates are used as the winding core 21, and the positive electrode 2 and the negative electrode 3 are wound with the separator 4 interposed therebetween.
- the separator 4, one of the positive electrode 2 or the negative electrode 3, another separator 4, and the other of the positive electrode 2 or the negative electrode 3 are arranged in this order, and the end portions of the two separators 4 are The sheet is sandwiched between the cores 21.
- the wound electrode group 20 is configured.
- the space between the two cores 21 is widened to release the end of the separator 4 and the core 21 is extracted from the electrode group 20 in the direction of arrow A.
- FIG. 3 is a schematic cross-sectional view of the separator 4.
- the separator 4 includes a porous film 12 and a lubricating layer 14 containing particulate matter 22 disposed on the surface thereof.
- the illustrated porous film 12 includes, for example, a porous polyolefin layer 16 mainly composed of polyethylene (PE), and a heat-resistant porous layer 18 interposed between the polyolefin layer 16 and the lubricating layer 14. To do.
- the heat resistant porous layer 18 contains, for example, polyamide as a main component.
- the heat-resistant porous layer 18 is formed only on one side of the polyolefin layer 16, and the lubricating layer 14 is formed on the surface of the heat-resistant porous layer 18.
- the heat resistant porous layer 18 may be formed on both surfaces of the polyolefin layer 16.
- the lubricating layer 14 may be formed on at least one surface of the porous film 12 or may be formed on both surfaces.
- the heat resistant porous layer 18 may be formed on both surfaces of the polyolefin layer 16, and the lubricating layer 14 may be formed on the surface of one heat resistant porous layer 18.
- FIG. 3 schematically shows an example of the arrangement of the heat-resistant porous layer 18 and the lubricating layer 14, and the ratio of the thickness of each layer does not necessarily match the actual one.
- the lubricating layer 14 is provided on the surface of the base material 12 so that the core is smoothly extracted after the electrode group 20 is configured. Therefore, the lubricating layer 14 is not necessarily provided on the entire separator 14, and may be provided only on a portion that contacts the winding core when winding. In addition, a lubricating layer is disposed in a portion that contacts the core of the separator 4, for example, a portion that is disposed on the innermost periphery of the electrode group of the separator 4, and other than the innermost periphery (intervening between the positive electrode and the negative electrode). The lubricating layer does not have to be disposed in the portion).
- the lubricating layer 14 may be formed only on the part of the separator 4 that contacts the side end of the core.
- the lubricating layer 14 is formed by disposing, for example, a particulate material 22 such as polytetrafluoroethylene particles on the surface of the heat resistant porous layer 18.
- the lubrication layer 14 is formed by applying a dispersion containing the particulate matter 22 to the surface of the heat resistant porous layer 18 and drying to adhere the particulate matter 22 to the surface of the heat resistant porous layer 18. May be.
- a dispersion an aqueous dispersion containing a surfactant can be used as the dispersion.
- the lubricating layer 14 does not contain a binder such as resin, and the particulate matter 22 adheres to the surface of the polyolefin layer 16 or the heat-resistant porous layer 18 due to the action of electrostatic force or surfactant. It is formed. The particles of the particulate substance 22 are aggregated with each other due to the electrostatic force or the action of the surfactant. Therefore, the lubricating layer 14 has high slipperiness due to the movement of the particulate matter 22 with an external force of rubbing with a finger. That is, the particulate matter 22 is disposed so as to be movable with respect to the porous film 12.
- the lubricating layer 14 has a specific surface roughness due to the particulate matter 22 being disposed on the surface of the porous film 12.
- the surface roughness of the lubricating layer 14 is set such that the surface roughness Sa (three-dimensional surface roughness) is 0.15 to 1.45 ⁇ m, for example, in the initial state immediately after drying or before constituting the electrode group. Yes.
- L x is the measurement length in the X direction
- Ly is the measurement length in the Y direction.
- the three-dimensional surface roughness Sa of the lubricating layer is preferably 0.18 to 1.42 ⁇ m, more preferably 0.19 to 1.41 ⁇ m, and particularly 0.2 to 1.4 ⁇ m.
- the surface roughness Sa is less than 0.15 ⁇ m, the slipperiness decreases as the contact area between the core 21 and the lubricating layer 14 increases.
- the surface roughness Sa exceeds 1.45 ⁇ m, the amount of the particulate matter 22 falling from the lubricating layer 14 increases, or the distance between the positive electrode 2 and the negative electrode 3 arranged with the separator 4 interposed therebetween is increased. It becomes non-uniform. As a result, battery characteristics may be impaired.
- the three-dimensional surface roughness can be adjusted by appropriately selecting the kind, shape, size (particle diameter, etc.) of the particulate matter, the weight of the particulate matter contained in the lubricating layer, and the like. For example, the size of the particulate matter and / or the weight of the particulate matter in the lubricating layer is adjusted.
- the particulate material 22 is not limited to the polytetrafluoroethylene, and particulate materials such as organic polymer compounds and inorganic compounds can be used.
- the particulate matter 22 is preferably electrochemically stable because the particulate matter 22 that has fallen may come into contact with the positive electrode 2 or the negative electrode 3 with the use of the secondary battery.
- the particulate matter 22 contacts the nonaqueous electrolyte in the battery case 1, it is preferable that the particulate matter 22 is stable with respect to a solvent (such as an organic solvent) contained in the nonaqueous electrolyte.
- the organic polymer compound constituting the particulate material 22 include, for example, a halogen atom-containing polymer such as a fluorine-containing polymer (a homopolymer or a copolymer containing a halogen atom-containing olefin such as vinyl halide as a constituent monomer) ), Polyolefins (olefins such as polyethylene, polypropylene, and ethylene-propylene copolymers, or copolymers), and polyesters (polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate).
- a halogen atom-containing polymer such as a fluorine-containing polymer (a homopolymer or a copolymer containing a halogen atom-containing olefin such as vinyl halide as a constituent monomer)
- Polyolefins olefins such as polyethylene, polypropylene, and ethylene-propy
- fluorine-containing polymers such as fluorine-containing polymers having a small wear coefficient
- polyolefins are preferred.
- Preferred fluorine-containing polymers include, for example, fluoroolefins such as polytetrafluoroethylene (PTFE) and perfluoroethylenepropylene copolymer (FEP), or olefins such as ethylene-tetrafluoroethylene copolymer (ETFE).
- PTFE polytetrafluoroethylene
- FEP perfluoroethylenepropylene copolymer
- ETFE ethylene-tetrafluoroethylene copolymer
- PFA perfluoroalkoxyalkane polymer
- the inorganic compound examples include an oxide of at least one element selected from silicon, aluminum, titanium, magnesium, zirconium, calcium, and the like (for example, silica, alumina, titania, magnesia, zirconia, calcium oxide), the element And nitrides or carbonates, and silicate minerals such as talc and mica.
- the oxides or carbonates for example, SiO 2 , Al 2 O 3 , TiO 2 , MgO, ZrO 2 , CaO, CaCO 3
- talc, mica, and the like are exemplified. preferable.
- the particulate matter organic polymer compound and / or inorganic compound
- the particulate matter 22 may be, for example, a short fiber or needle shape, but is usually a granular material having a spherical shape, a spheroidal shape, a plate shape, a rod shape, or the like.
- the particulate material 22 is preferably a spherical (such as a sphere having an average aspect ratio of 1 to 2 or a substantially spherical shape).
- the average particle size (median diameter in the volume-based particle size distribution) of the particulate material 22 is, for example, 0.01 to 1 ⁇ m, preferably 0.02 to 0.9 ⁇ m, and more preferably 0.03 to 0.8 ⁇ m. . If the average particle size is too small, the surface of the lubricating layer 14 becomes flat and it becomes difficult to adjust the surface roughness Sa. If the average particle size of the particulate material 22 is too large, the surface roughness Sa increases, but the exposed portion of the porous film 12 increases, and the slipperiness due to the lubricating layer 14 may decrease.
- the particulate matter 22 may be used by mixing two or more kinds of particles having different average particle diameters and / or materials.
- the weight (dry weight) of the particulate material 22 of the lubricating layer 14 contained per 1 m 2 of the surface of the porous film 12 depends on the kind of the particulate material, but is, for example, in the range of 0.1 to 2 g. It can be selected, preferably 0.1 to 1.5 g, more preferably 0.2 to 1 g, especially 0.2 to 0.8 g. If the weight of the particulate matter 22 per unit area of the lubricating layer 14 is too small, the area in which the porous film 12 having a low slip property and the core 21 are in direct contact with each other increases, and the drawability of the core 21 decreases. There is a case.
- the lubricating layer 14 only needs to be able to dispose the particulate material 22 on the surface of the porous film 12, and is not limited to the above-described application, and can also be formed by a printing method, a spray method, or the like.
- the particulate matter 22 is usually disposed by applying a dispersion liquid in which the particulate matter is dispersed in a dispersion medium to the surface of the porous film 12 by the above-described method such as coating, and further drying the dispersion medium. Can do.
- dispersion medium examples include water, alcohols such as methanol, ethanol, and ethylene glycol (such as C 2-4 alkanol or C 2-4 alkanediol); ketones such as acetone; ethers such as diethyl ether; nitriles such as acetonitrile; Examples thereof include N-methyl-2-pyrrolidone (NMP).
- alcohols such as methanol, ethanol, and ethylene glycol (such as C 2-4 alkanol or C 2-4 alkanediol)
- ketones such as acetone
- ethers such as diethyl ether
- nitriles such as acetonitrile
- examples thereof include N-methyl-2-pyrrolidone (NMP).
- NMP N-methyl-2-pyrrolidone
- the dispersion may contain a surfactant if necessary.
- Surfactants include anionic surfactants such as alkyl sulfate esters, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, sorbitan fatty acid esters, and cationic surfactants such as alkylamine salts. Examples thereof include amphoteric surfactants such as surfactants and alkylbetaines. Surfactants can be used singly or in combination of two or more.
- the ratio of the surfactant is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the particulate matter in terms of solid content.
- the drying temperature and time can be appropriately selected according to the volatility of the dispersion medium.
- the average thickness of the lubricating layer 14 is, for example, 0.05 to 3 ⁇ m, preferably 0.05 to 2.5 ⁇ m, more preferably 0.05 to 2 ⁇ m, or 0.3 to 2 ⁇ m.
- the average thickness can be determined by a known method, for example, non-contact surface shape measurement using a laser beam or an electron beam.
- the separator of the present invention is particularly advantageous when producing an electrode group of a square battery. Deformation of the electrode group accompanying pulling of the winding core (the innermost part of the electrode group is dragged out together with the winding core and protrudes from the end portion, etc.) is suppressed. When the electrode group is greatly deformed by pulling out the winding core, a large frictional force acts between the winding core and the separator, and the possibility that the separator is damaged increases. Therefore, by suppressing the deformation of the electrode group, a highly reliable electrode group can be manufactured.
- porous film 12 only needs to have a porous polyolefin layer 16, and does not necessarily have to include the heat resistant porous layer 18.
- the porous film 12 is formed of only the polyolefin layer 16, the lubricating layer 14 is formed on at least one surface of the polyolefin layer 16.
- the polyolefin layer 16 is a porous layer containing, in addition to the PE, for example, a polyolefin such as polypropylene (PP) or an ethylene-propylene copolymer, or a polyolefin such as a copolymer thereof.
- a polyolefin such as polypropylene (PP) or an ethylene-propylene copolymer
- PP polypropylene
- ethylene-propylene copolymer ethylene-propylene copolymer
- a polyolefin such as a copolymer thereof.
- the polyolefin layer may contain other polymers together with the polyolefin. Softening, melting, or shrinkage of the polyolefin layer 16 may be prevented by selecting other polymer types and / or amounts used.
- polystyrene rubber-containing polystyrene, styrene polymers such as acrylonitrile-styrene copolymers; polyesters such as polyethylene terephthalate; polyamides such as polyamide 6 and polyamide 12; acrylic polymers such as polymethyl methacrylate; cellulose derivatives; Examples thereof include thermoplastic polymers such as plastic elastomers.
- the proportion of polyolefin in the porous film is, for example, 50 to 100% by weight.
- the thickness of the polyolefin layer is preferably in the range of 5 to 200 ⁇ m.
- the average pore size of the polyolefin layer is preferably 0.05 to 2 ⁇ m.
- the porosity of the polyolefin layer is preferably 25 to 75% by volume, for example.
- a commercially available porous film may be used, and a polymer material (polymer material including polyolefin) as a raw material by a known porous film molding method (extrusion molding, blow molding, inflation molding, coating method, etc.) ) May be formed and stretched.
- the stretching process may be either uniaxial or biaxial stretching.
- a known pore agent or the like may be used for film formation.
- the porous film 12 may have a heat-resistant porous layer 18.
- a heat-resistant porous layer 18 When the proportion of polyolefin contained in the polyolefin layer 16 is large, it is advantageous to form the heat-resistant porous layer 18 on the surface.
- the heat resistant porous layer 18 (or a material constituting the heat resistant porous layer) has a higher melting point or heat distortion temperature than the polyolefin layer.
- Such a heat-resistant porous layer usually contains a high heat-resistant polymer.
- heat-resistant polymers include polyolefins having a melting point of 150 ° C. or higher such as PP; amide bond-containing polymers such as polyamides, polyamide copolymers, and aramids; polyvinylidene fluoride (PVDF), vinylidene fluoride and propylene hexafluoride (HFP) Fluorine-containing polymers such as copolymers (PVDF-HFP) and PTFE; Polymers containing imide bonds such as polyimide (PI), polyamideimide (PAI) and polyetherimide (PEI); polyethylene terephthalate (PET), polypropylene terephthalate (PPT) ), Polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), etc.
- PI polyimide
- PAI polyamideimide
- PPT polyetherimide
- PET poly
- Polyarylate polymers having sulfone groups such as polysulfone (PSF), polyethersulfone (PES); polyphenylene ether (PPE); polycarbonate (PC); polyphenylene sulfide (PPS); polyetherketone (PEK) and Aromatic polyether ketone polymers such as polyether ether ketone (PEEK); polyacetal (POM); polyether nitrile (PEN) and the like.
- the heat resistant porous layer 18 may contain the above polymers alone or in combination of two or more thereof. In addition, you may use another polymer together with the said polymer.
- at least one selected from the group consisting of an amide bond-containing polymer, a fluorine-containing polymer, an imide bond-containing polymer, and a polyolefin is preferable.
- PP, PVDF, PVDF-HFP, PI, PAI, and aramid are preferable.
- the melting point or heat distortion temperature of the polymer material constituting the heat resistant porous layer is, for example, greater than 150 ° C. and 800 ° C. or less.
- the heat resistant porous layer 18 may contain an inorganic filler, if necessary.
- an inorganic filler the inorganic compounds exemplified above can be used.
- ceramic particles such as silica, alumina, titania, magnesia, zirconia are particularly preferable.
- the average particle size of the inorganic filler is preferably 0.001 to 2 ⁇ m.
- the proportion of the inorganic filler is 1 to 1000 parts by weight, preferably 10 to 700 parts by weight, and more preferably 50 to 500 parts by weight with respect to 100 parts by weight of the raw material polymer constituting the heat resistant porous layer 18.
- the thickness of the heat-resistant porous layer 18 can be selected from the range of 0.01 to 50 ⁇ m, preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m.
- the average pore diameter and porosity of the heat-resistant porous layer 18 can be appropriately selected from the same range as that of the porous film.
- the heat-resistant porous layer 18 can be formed by applying a coating liquid containing a raw material polymer to a porous polyolefin layer by a known coating method and drying.
- a coating liquid a solution or dispersion containing a raw material polymer can be used.
- the solvent for the coating solution examples include alcohols such as methanol, ethanol, and ethylene glycol (C 2-4 alkanol or C 2-4 alkanediol); ketones such as acetone; ethers such as diethyl ether and tetrahydrofuran; amides such as dimethylformamide Nitriles such as acetonitrile; sulfoxides such as dimethyl sulfoxide; N-methyl-2-pyrrolidone (NMP) and the like. These solvents can be used alone or in combination of two or more.
- alcohols such as methanol, ethanol, and ethylene glycol (C 2-4 alkanol or C 2-4 alkanediol)
- ketones such as acetone
- ethers such as diethyl ether and tetrahydrofuran
- amides such as dimethylformamide Nitriles such as acetonitrile
- sulfoxides such as dimethyl sulfoxide
- NMP N
- the raw material polymer constituting the polyolefin layer 16 and the raw material polymer constituting the heat resistant porous layer 18 are coextruded and stretched to form a laminated film of the polyolefin layer 16 and the heat resistant porous layer 18. May be.
- the total thickness of the separator is, for example, 5.05 to 250 ⁇ m, or 5.05 to 50 ⁇ m.
- the positive electrode 2 includes a positive electrode current collector and a positive electrode active material layer carried thereon.
- a known positive electrode current collector for non-aqueous secondary battery applications for example, a metal foil formed of aluminum, aluminum alloy, stainless steel, titanium, titanium alloy, or the like can be used.
- the thickness of the positive electrode current collector is, for example, 1 to 100 ⁇ m, preferably 5 to 70 ⁇ m, and more preferably 10 to 50 ⁇ m.
- any material that can occlude / release lithium ions can be used without particular limitation.
- the positive electrode active material layer contains a conductive material, a binder and the like in addition to the positive electrode active material.
- conductive materials include carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; various graphites such as natural graphite and artificial graphite; and conductive fibers such as carbon fiber and metal fiber.
- the binder for the positive electrode include, for example, polyvinylidene fluoride (PVdF), modified polyvinylidene fluoride, fluororesin such as polytetrafluoroethylene (PTFE); styrene butadiene copolymer rubber particles (SBR) or a modified product thereof.
- Rubber particle binder having an acrylate unit; cellulose derivatives such as carboxymethylcellulose (CMC), and the like can be used.
- the thickness of the positive electrode active material layer is not particularly limited, but is, for example, 0.1 to 150 ⁇ m, preferably 1 to 100 ⁇ m, and more preferably 10 to 90 ⁇ m.
- the negative electrode 3 is composed of a negative electrode current collector and a negative electrode active material layer carried thereon.
- a known negative electrode current collector for non-aqueous secondary battery applications for example, a metal foil formed of copper, copper alloy, nickel, nickel alloy, stainless steel, or the like can be used.
- the thickness of the negative electrode current collector is, for example, 1 to 100 ⁇ m, preferably 2 to 50 ⁇ m, and more preferably 5 to 30 ⁇ m.
- a metal including at least one selected from the group consisting of Li, Al, Zn, Sn, In, Si, Ta, and Nb, an alloy thereof, and an oxide (for example, SiO 0.3 , Ta 2 O 5 , Nb 2 O 5 ), carbon materials such as graphite and carbon nanotubes, lithium titanium oxide having a spinel structure such as Li 4 Ti 5 O 12 , Li 4 Fe 0.5 Ti 5 O 12 , Li 4 Zn 0.5 Ti 5 O 12 Products, sulfides such as TiS 2 , nitrogen compounds such as LiCo 2.6 O 0.4 N and Ta 3 N 5 , mixtures thereof, and those obtained by adding various metal elements to these materials.
- any material that can occlude and release lithium ions can be used for the negative electrode without any particular limitation.
- the negative electrode active material layer may include a negative electrode conductive material (such as the conductive material exemplified in the positive electrode conductive material) and / or a negative electrode binder (the positive electrode binder).
- a negative electrode conductive material such as the conductive material exemplified in the positive electrode conductive material
- a negative electrode binder the positive electrode binder
- An exemplary binder may be contained.
- the thickness of the negative electrode active material layer is not particularly limited, but is, for example, 0.1 to 150 ⁇ m, preferably 1 to 120 ⁇ m, and more preferably 10 to 100 ⁇ m.
- the positive electrode 2 and the negative electrode 3 are not particularly limited, but the positive electrode active material or the negative electrode active material is supported on each current collector by a coating method, a sputtering method and a vapor deposition method, an aerosol vapor deposition method, a CVD method, a screen printing method, or the like. Can be produced.
- the positive electrode or the negative electrode active material layer may be formed on one side of the current collector or on both sides.
- Nonaqueous electrolyte It is desirable to use a non-aqueous solvent for the non-aqueous electrolyte in order to use lithium ions for charging and discharging. More preferably, the solvent has high ion conductivity when mixed with a lithium salt.
- ethylene carbonate (EC), propylene carbonate (PC), ⁇ -butyrolactone (GBL), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and the like are preferable. You may use a solvent by 1 type or in mixture of 2 or more types. It is also more preferable to use a mixed solvent containing EC which is a high dielectric constant solvent.
- the lithium salt used for the non-aqueous electrolyte is not particularly limited as long as it can be dissolved in the above non-aqueous solvent and can be used as an electrolyte for a lithium secondary battery.
- the lithium salt for example, LiPF 6 , LiBF 4 , LiClO 4 , LiN (C 2 F 5 SO 2 ) 2 , and LiN (CF 3 SO 2 ) 2 are preferable. These lithium salts can be used alone or in combination of two or more. Since LiBF 4 has a lower ionic conductivity than LiPF 6 and LiClO 4 when dissolved in a non-aqueous solvent, it is preferably used in combination with other lithium salts.
- the lithium salt concentration in the nonaqueous electrolyte is, for example, 0.1 to 3 mol / L, preferably 0.2 to 2.5 mol / L, and more preferably 0.5 to 2 mol / L.
- the non-aqueous electrolyte has a low ionic conductivity when the concentration is low, and it becomes difficult to dissociate ions when the concentration is high. Accordingly, the ion conductivity tends to decrease if the lithium salt concentration is too high or too low.
- Example 1 The separator 4 shown in FIG. 3 was produced according to the procedure shown below.
- a porous film containing polyamide having a thickness of 3.5 ⁇ m was formed on one surface of the polyolefin layer 16.
- the porous membrane containing polyamide was formed by applying a solution obtained by dissolving polyamide in N-methyl-2-pyrrolidone (NMP) to one side of the polyolefin layer 16 and drying.
- NMP N-methyl-2-pyrrolidone
- 200 parts by weight of inorganic oxide (alumina having an average particle diameter of 0.013 ⁇ m) was dispersed per 100 parts by weight of polyamide.
- a PTFE spherical particle (particulate matter 22) having an average particle size of 0.2 ⁇ m is dispersed in a mixture of a surfactant and water to prepare a dispersion, and the dispersion is used as a heat resistant porous layer. 18 surfaces were coated. Thereafter, water was evaporated to form the lubricating layer 14.
- the dry weight of the particulate matter 22 contained in the lubricating layer 14 was 0.5 g per 1 m 2 of the surface of the heat resistant porous layer 18 (that is, the surface of the porous film 12). Further, the surface roughness Sa of the lubricating layer 14 measured by an electron beam three-dimensional roughness analyzer (ERA-8800 manufactured by Elionix Co., Ltd.) was 1.0 ⁇ m. The acceleration voltage at this time was 5 kV, and the observation magnification was 200 times.
- the positive electrode 2 was produced as follows. Lithium cobaltate (LiCoO 2 ) as a positive electrode active material, acetylene black (AB) as a conductive additive, and PVDF as a binder are mixed in a weight ratio of 100: 4: 3, and NMP is used as a solvent. A slurry was prepared.
- This slurry was applied to both surfaces of an aluminum foil (thickness: 15 ⁇ m) as a positive electrode current collector, dried in an atmosphere at 110 ° C. for 30 minutes, and then rolled to produce positive electrode 2.
- the thickness of the positive electrode 2 was 160 ⁇ m.
- the negative electrode 3 was produced as follows. Artificial graphite as a negative electrode active material, a styrene-butadiene copolymer rubber particle binder as a binder, and carboxymethyl cellulose (CMC) as a thickener are mixed at a weight ratio of 100: 1: 1, A slurry was prepared using water as a dispersion medium.
- CMC carboxymethyl cellulose
- This slurry was applied to both sides of a copper foil (thickness 10 ⁇ m) as a current collector for the negative electrode, dried in an atmosphere of 110 ° C. for 30 minutes, and then rolled to prepare the negative electrode 3.
- the thickness of the negative electrode 3 was 180 ⁇ m.
- the space between the two cores 21 is widened, and as shown in FIG.
- the core 21 was extracted in the direction A from the inside. At that time, whether or not the winding core 21 was smoothly removed was observed, and an appearance inspection of the produced electrode group 20 was performed.
- the electrode group 20 was inserted into a bottomed square aluminum battery case having an opening. A non-aqueous electrolyte was injected into case 1 and the opening was sealed to produce 1,000 lithium secondary batteries. At this time, the electrode group 20 used only what passed the above-mentioned external appearance test.
- a non-aqueous electrolyte a solution prepared by dissolving LiPF 6 as a lithium salt at a concentration of 1 mol / L in a solvent prepared by mixing ethylene carbonate (EC) and propylene carbonate (PC) at a volume ratio of 1: 3. It was used.
- a charge / discharge test for evaluating battery characteristics was performed on the manufactured 1,000 lithium secondary batteries.
- each battery was charged with a current of 2 hours until the voltage between the terminals reached 4.2V, and then discharged until the voltage between the terminals decreased to 3.0V.
- the pause time between charging and discharging was 30 minutes.
- the discharge capacity after repeating this charging / discharging 200 times was measured, the measured value was compared with the measured value of the initial discharge capacity, and the index with the initial discharge capacity being 100 was calculated. If the index was 70 or more, it was judged that the battery characteristics were good.
- Example 2 As the particulate material 22, spherical particles of perfluoroethylenepropylene copolymer (FEP) having an average particle diameter of 0.2 ⁇ m are used, and the dry weight of the particulate material 22 in the lubricating layer 14 is 0.8 g / m 2 . Except for the change, 1,000 lithium secondary batteries were produced in the same manner as in Example 1. The surface roughness Sa of the formed lubricating layer 14 was 1.4 ⁇ m.
- FEP perfluoroethylenepropylene copolymer
- Example 1 In the same manner as in Example 1, when the electrode group 20 was configured, the state of extraction of the core 21 was observed, and an appearance inspection of the produced electrode group 20 was performed. Further, the battery characteristics were evaluated in the same procedure as in Example 1.
- Example 3 Implementation was carried out except that spherical particles of SiO 2 having an average particle diameter of 0.1 ⁇ m were used as the particulate matter 22 and the dry weight of the particulate matter 22 in the lubricating layer 14 was changed to 0.3 g / m 2.
- a lithium secondary battery was produced in the same manner as in Example 1.
- the surface roughness Sa of the formed lubricating layer 14 was 0.2 ⁇ m.
- Example 1 In the same manner as in Example 1, when the electrode group 20 was configured, the state of extraction of the core 21 was observed, and an appearance inspection of the produced electrode group 20 was performed. Further, the battery characteristics were evaluated in the same procedure as in Example 1.
- Comparative Example 1 Except that PTFE spherical particles having an average particle diameter of 0.2 ⁇ m were used as the particulate matter 22 and the dry weight of the particulate matter 22 in the lubricating layer 14 was changed to 2.0 g / m 2. In the same manner as in Example 1, a lithium secondary battery was produced. The surface roughness Sa of the formed lubricating layer 14 was 1.5 ⁇ m.
- Example 2 In the same manner as in Example 1, when forming the electrode group 20, the state of extraction of the core 21 was observed, and an appearance inspection of the manufactured electrode group 20 was performed. Further, the battery characteristics were evaluated in the same procedure as in Example 1.
- Comparative Example 2 >> Except that PTFE spherical particles having an average particle diameter of 0.2 ⁇ m are used as the particulate matter 22 and the dry weight of the particulate matter 22 in the lubricating layer 14 is changed to 0.1 g / m 2. In the same manner as in Example 1, a lithium secondary battery was produced. The surface roughness Sa of the formed lubricating layer 14 was 0.1 ⁇ m.
- Example 2 In the same manner as in Example 1, when forming the electrode group 20, the state of extraction of the core 21 was observed, and an appearance inspection of the manufactured electrode group 20 was performed. Further, the battery characteristics were evaluated in the same procedure as in Example 1.
- Comparative Example 3 A lithium secondary battery was produced in the same manner as in Example 1 except that a separator composed only of the porous film 12 was produced without forming the lubricating layer 14.
- Example 2 In the same manner as in Example 1, when forming the electrode group 20, the state of extraction of the core 21 was observed, and an appearance inspection of the manufactured electrode group 20 was performed. Further, the battery characteristics were evaluated in the same procedure as in Example 1.
- Example 4 A lithium secondary battery was produced in the same manner as in Example 1 except that when the electrode group 20 was formed, the lubricating layer 14 was formed only on the portion of the porous film 12 that was in contact with the core 21.
- Example 2 In the same manner as in Example 1, when forming the electrode group 20, the state of extraction of the core 21 was observed, and an appearance inspection of the manufactured electrode group 20 was performed. Further, the battery characteristics were evaluated in the same procedure as in Example 1.
- Example 4 in which the lubricating layer 14 was formed only on the portion of the porous film 12 that was in contact with the core 21 when constituting the electrode group 20, the same results as in the other examples were obtained. From this, in order to achieve the effect of the present invention, it is understood that it is sufficient that the lubricating layer 14 is formed in a portion in contact with the core 21 of the separator 14.
- Comparative Example 1 in which the surface roughness Sa of the lubricating layer 14 is 1.5 ⁇ m, the winding core 21 is smoothly extracted from the electrode group 20, and an electrode having an abnormality in the appearance inspection is also obtained. Group 20 did not exist. However, regarding the result of the charge / discharge test, there was a lithium secondary battery in which the charge / discharge cycle characteristics were lowered only in Comparative Example 1.
- the lubricating layer 14 is formed so that the surface roughness Sa is in the range of more than 0.1 ⁇ m and less than 1.5 ⁇ m, so that sufficient slipping property with respect to the core 21 of the separator 4 is ensured.
- the formation of the lubricating layer 14 is preferable from the viewpoint of not adversely affecting the battery characteristics.
- the lithium secondary battery separator of the present invention exhibits good core pullability even when the electrode and separator are wound more closely when forming the electrode group. Therefore, it is useful as a separator for a lithium secondary battery in which high capacity and high output are particularly required as a power source for mobile devices and the like.
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Abstract
Description
図1は、本発明の実施形態の一例を示す角型のリチウム二次電池の概略横断面図である。
電池10は、薄い箱形の電池ケース1と、ケース1内に収納された電極群20及び図示しない非水電解質とで構成されている。前記電極群20は、矩形の平坦面及びこの平坦面の両端に位置する湾曲面を有する側面を具備している。
図示例の多孔質フィルム12は、例えばポリエチレン(PE)を主成分とする多孔質のポリオレフィン層16と、ポリオレフィン層16と前記潤滑層14との間に介在する耐熱性多孔質層18とを具備する。耐熱性多孔質層18は、例えばポリアミドを主成分として含有する。
角型電池の場合には、セパレータ4の最内周面とこの最内周面と接する巻芯21の側端部との間に特に大きな摩擦力が発生する。そのため巻芯の側端部と接触するセパレータ4の部分にだけ潤滑層14を形成するようにしてもよい。
潤滑層14の表面粗さは、例えば乾燥直後の初期状態又は電極群を構成する前で、表面粗さSa(三次元表面粗さ)が0.15~1.45μmとなるように設定されている。
(潤滑層)
潤滑層の前記三次元表面粗さSaは、好ましくは0.18~1.42μm、さらに好ましくは0.19~1.41μm、特に、0.2~1.4μmである。表面粗さSaが0.15μm未満では、巻芯21と潤滑層14との接触面積の増大に伴い、すべり性が低下する。
一方、表面粗さSaが1.45μmを超えると、潤滑層14からの粒子状物質22の脱落量が増大したり、セパレータ4を挟んで配置される正極2と負極3との間の距離が不均一となる。この結果、電池特性を損なう可能性がある。
上記粒子状物質(有機高分子化合物及び/又は無機化合物)は、一種で又は二種以上組み合わせて使用できる。
粒子状物質22は、平均粒径及び/又は材質の異なる2種類以上の粒子を混合して使用してもよい。
潤滑層14の単位面積当たりの粒子状物質22の重量が小さすぎると、すべり性が小さい多孔質フィルム12と巻芯21とが直接に接触する面積が増大し、巻芯21の抜き取り性が低下する場合がある。
粒子状物質22は、通常、粒子状物質を分散媒に分散させた分散液を、多孔質フィルム12の表面に、塗布などの上記方法により適用し、さらに分散媒を乾燥することにより配置させることができる。
乾燥温度及び時間は、分散媒の揮発性に応じて、適宜選択できる。
潤滑層14の平均厚みは、例えば、0.05~3μm、好ましくは0.05~2.5μm、さらに好ましくは0.05~2μm、又は0.3~2μmである。
平均厚みは、公知の方法、例えば、レーザー光線や電子線による非接触表面形状測定などにより求めることができる。
多孔質フィルム12は、多孔質のポリオレフィン層16を有していればよく、必ずしも耐熱多孔質層18を備える必要はない。多孔質フィルム12をポリオレフィン層16だけで形成する場合には、ポリオレフィン層16の少なくとも一方の表面に、潤滑層14が形成される。
ポリオレフィン層16は、前記PEの他、例えば、ポリプロピレン(PP)、エチレン-プロピレン共重合体などのポリオレフィンもしくはそれらの共重合体などのポリオレフィンを含む多孔質層である。
多孔質フィルム中のポリオレフィンの割合は、例えば、50~100重量%である。
ポリオレフィン層の平均孔径は、0.05~2μmが好ましい。
ポリオレフィン層の空孔率は、例えば、25~75体積%が好ましい。
ポリオレフィン層16の収縮を防止する観点から、多孔質フィルム12は、耐熱性多孔質層18を有してもよい。ポリオレフィン層16に含まれるポリオレフィンの割合が多い場合、耐熱性多孔質層18を表面に形成することが有利である。耐熱性多孔質層18(又は耐熱性多孔質層を構成する材料)は、前記ポリオレフィン層よりも高い融点又は熱変形温度を有する。このような耐熱性多孔質層は、通常、高い耐熱性ポリマーを含有する。
上記ポリマーのうち、アミド結合含有ポリマー、フッ素含有ポリマー、イミド結合含有ポリマー、およびポリオレフィンよりなる群から選択される少なくとも1種が好ましい。特に、PP、PVDF、PVDF-HFP、PI、PAI、およびアラミドなどが好ましい。
無機フィラーの割合は、耐熱性多孔質層18を構成する原料ポリマー100重量部に対して、1~1000重量部、好ましくは10~700重量部、さらに好ましくは50~500重量部である。
耐熱性多孔質層18の平均孔径及び空孔率は、前記多孔質フィルムと同様の範囲から適宜選択できる。
セパレータ全体の厚みは、例えば、5.05~250μm、又は5.05~50μmである。
(正極及び負極)
正極2は、正極用の集電体と、それに担持される正極活物質層とから構成される。正極集電体としては、非水系二次電池用途で公知の正極集電体、例えば、アルミニウム、アルミニウム合金、ステンレス鋼、チタン、チタン合金などで形成された金属箔などが使用できる。正極集電体の厚みは、例えば、1~100μm、好ましくは5~70μm、さらに好ましくは10~50μmである。
正極又は負極活物質層は、それぞれ、集電体の片面に形成してもよく、両面に形成してもよい。
非水電解質には、充放電にリチウムイオンを利用するために非水溶媒を用いることが望ましい。溶媒は、リチウム塩を混合したときのイオン伝導度が高くなるものがより好ましい。例えばエチレンカーボネート(EC)、プロピレンカーボネート(PC)、γ-ブチロラクトン(GBL)、エチルメチルカーボネート(EMC)、ジエチルカーボネート(DEC)、およびジメチルカーボネート(DMC)等が好ましい。溶媒は、一種で又は二種以上混合して使用してもよい。高誘電率溶媒であるECを含む混合溶媒を用いることも、より好ましい。
《実施例1》
以下に示す手順で、図3に示すセパレータ4を作製した。
(1)ポリオレフィン層16として、厚さが20μmの多孔質ポリエチレンフィルムを使用した。このフィルムは、ポリエチレンを溶融押出しで成形し、得られた成形物を2軸延伸して作製したものである。その孔径は、正極2および負極3より脱離した活物質、結着剤および導電剤などが透過しないように0.1~1μmとした。
電極群20を、開口部を有する有底角型のアルミニウム製電池ケースに挿入した。ケース1に、非水電解質を注入し、開口部を封口して、1千個のリチウム二次電池を作製した。このとき、電極群20は、上記した外観検査に合格したもののみを使用した。非水電解質としては、エチレンカーボネート(EC)とプロピレンカーボネート(PC)とを体積比で1:3の割合で調合した溶媒に、リチウム塩としてのLiPF6を1mol/Lの濃度で溶解させたものを使用した。
粒子状物質22として、平均粒径0.2μmを有するパーフルオロエチレンプロピレンコポリマー(FEP)の球状粒子を使用するとともに、潤滑層14中の粒子状物質22の乾燥重量を0.8g/m2に変更した以外は、実施例1と同様にして1千個のリチウム二次電池を作製した。形成された潤滑層14の表面粗さSaは、1.4μmであった。
粒子状物質22として、平均粒径0.1μmを有するSiO2の球状粒子を使用するとともに、潤滑層14中の粒子状物質22の乾燥重量を0.3g/m2に変更した以外は、実施例1と同様にしてリチウム二次電池を作製した。形成された潤滑層14の表面粗さSaは、0.2μmであった。
粒子状物質22として、平均粒径0.2μmを有するPTFEの球状粒子を使用するとともに、潤滑層14中の粒子状物質22の乾燥重量を2.0g/m2に変更した以外は、実施例1と同様にしてリチウム二次電池を作製した。形成された潤滑層14の表面粗さSaは1.5μmであった。
粒子状物質22として、平均粒径0.2μmを有するPTFEの球状粒子を使用するとともに、潤滑層14中の粒子状物質22の乾燥重量を0.1g/m2に変更した以外は、実施例1と同様にしてリチウム二次電池を作製した。形成された潤滑層14の表面粗さSaは、0.1μmであった。
潤滑層14を形成することなく、多孔質フィルム12のみからなるセパレータを作製した以外は、実施例1と同様にしてリチウム二次電池を作製した。
電極群20を形成するときに、多孔質フィルム12の巻芯21と接触する部分のみに、潤滑層14を形成したこと以外は、実施例1と同様にしてリチウム二次電池を作製した。
なお、抜き取り観察及び外観検査、電池特性は、下記の指標により評価した。
A:巻芯の抜き取りが円滑に行われ、抜き取りに追随してセパレータの最内部分が引き出されることはなかった。
B:巻芯の抜き取りに伴い、セパレータの最内部分が引き出されていた。
A:初期の放電容量を100としたとき、充放電の繰り返し後に測定した放電容量が70以上であった。
B:初期の放電容量を100としたとき、充放電の繰り返し後に測定した放電容量が70未満であった。
表1に示すように、潤滑層14の表面粗さSaが特定の範囲にある実施例1~4においては、それぞれ約1千個の電極群20について、巻芯21の抜き取り状態を観察した結果、全ての実施例について円滑な抜き取りが行われていた。また、作製された電極群20の外観検査の結果も、巻芯21の抜き取りに追随して、最内の部分が1mm以上引き出されているような外観不良を有する電極群20は存在しなかった。この結果は、潤滑層14の表面粗さSaが適度な大きさを有するために、潤滑層14が十分なすべり性を発揮したからであると考えられる。
2 正極
3 負極
4 セパレータ
10 リチウム二次電池
12 多孔質フィルム
14 潤滑層
18 耐熱性多孔質層
20 電極群
Claims (15)
- ポリオレフィン層を含む多孔質フィルムと、
前記多孔質フィルムの表面に配置された粒子状物質を含む潤滑層と、を具備し、
前記潤滑層の三次元表面粗さが、0.15~1.45μmである、リチウム二次電池用セパレータ。 - 前記潤滑層の三次元表面粗さが、0.2~1.4μmである、請求項1に記載のセパレータ。
- 前記粒子状物質は、静電力により、前記多孔質フィルムの表面に付着している、請求項1に記載のセパレータ。
- 前記潤滑層が、前記多孔質フィルムの表面の1m2あたり、前記粒子状物質0.1~2gを含む、請求項1に記載のセパレータ。
- 前記粒子状物質が、平均粒径0.01~1μmを有する、請求項1に記載のセパレータ。
- 前記粒子状物質が、有機高分子化合物及び無機化合物から選択される少なくとも1種を含む、請求項1記載のセパレータ。
- 前記有機高分子化合物が、フッ素含有ポリマーおよびポリオレフィンから選択される少なくとも1種を含む、請求項6記載のセパレータ。
- 前記無機化合物が、SiO2、Al2O3、TiO2、MgO、ZrO2、CaO、CaCO3、タルク、およびマイカよりなる群から選択される少なくとも1種を含む、請求項6記載のセパレータ。
- 前記多孔質フィルムが、更に、前記ポリオレフィン層と前記潤滑層との間に介在する耐熱性多孔質層を具備し、前記耐熱性多孔質層の融点又は熱変形温度が、前記ポリオレフィン層よりも高い、請求項1に記載のセパレータ。
- 前記耐熱性多孔質層が、アミド結合含有ポリマー、フッ素含有ポリマー、イミド結合含有ポリマー、およびポリオレフィンよりなる群から選択される少なくとも1種を含む、請求項1記載のセパレータ。
- 前記潤滑層が、平均厚み0.05~3μmを有し、前記ポリオレフィン層が、厚み5~200μmを有し、全体の厚みが5.05~250μmである、請求項1に記載のセパレータ。
- 正極、負極、および前記正極と前記負極との間に介在する請求項1に記載のセパレータを含む電極群、
非水電解質、ならびに
前記電極群と前記非水電解質とを収納する電池ケースを具備する、リチウム二次電池。 - 前記潤滑層が、前記セパレータの前記電極群の最内周に配置されている、請求項12記載のリチウム二次電池。
- 前記電極群が、矩形の平坦面および前記平坦面の両端に位置する湾曲面を有する側面を具備する、角形の請求項12記載のリチウム二次電池。
- 正極、負極、および前記正極と前記負極との間に介在するセパレータを含む電極群、
非水電解質、ならびに
前記電極群と前記非水電解質とを収納する電池ケースを具備し、
前記セパレータが、ポリオレフィン層を含む多孔質フィルムと、前記多孔質フィルムの表面に配置された粒子状物質を含む潤滑層とを具備し、
前記潤滑層が、前記セパレータの前記電極群の最内周に配置され、
前記電極群が、矩形の平坦面および前記平坦面の両端に位置する湾曲面を有する側面を具備する、角形のリチウム二次電池。
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CN112002865A (zh) * | 2020-08-25 | 2020-11-27 | 苏州捷力新能源材料有限公司 | 一种有机/无机复合多孔隔膜 |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09245762A (ja) * | 1996-03-11 | 1997-09-19 | Nitto Denko Corp | 電池用セパレータおよびその製造方法 |
JP2000007819A (ja) * | 1998-04-21 | 2000-01-11 | Tokuyama Corp | 多孔性フィルムおよびその製造方法 |
JP2000204174A (ja) * | 1999-01-13 | 2000-07-25 | Ube Ind Ltd | 多孔質フイルム及び電池用セパレ―タ |
JP2002117825A (ja) * | 2000-10-06 | 2002-04-19 | Denso Corp | 扁平形状巻回型電極体の製造方法 |
JP2002151044A (ja) * | 2000-08-30 | 2002-05-24 | Sumitomo Chem Co Ltd | 非水電解液二次電池用セパレータおよび非水電解液二次電池 |
JP2005171230A (ja) * | 2003-11-05 | 2005-06-30 | Toray Ind Inc | 二軸配向微多孔フィルムおよびその製造方法 |
JP2009070726A (ja) * | 2007-09-14 | 2009-04-02 | Teijin Ltd | 非水電解質電池の製造方法 |
JP2009238752A (ja) * | 2008-03-27 | 2009-10-15 | Samsung Sdi Co Ltd | 電極組立体及びこれを具備する二次電池 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW595035B (en) * | 2000-08-30 | 2004-06-21 | Sumitomo Chemical Co | Separator for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
US6692867B2 (en) * | 2001-10-12 | 2004-02-17 | Celgard Inc. | Battery separator-pin removal |
JP5095121B2 (ja) * | 2006-04-28 | 2012-12-12 | パナソニック株式会社 | 非水電解質二次電池用セパレータおよび非水電解質二次電池 |
-
2009
- 2009-04-07 JP JP2009093037A patent/JP2010244875A/ja not_active Withdrawn
-
2010
- 2010-04-06 KR KR1020117005237A patent/KR20110049857A/ko not_active Application Discontinuation
- 2010-04-06 WO PCT/JP2010/002519 patent/WO2010116729A1/ja active Application Filing
- 2010-04-06 CN CN2010800026209A patent/CN102160212A/zh active Pending
- 2010-04-06 US US13/062,151 patent/US20110159347A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09245762A (ja) * | 1996-03-11 | 1997-09-19 | Nitto Denko Corp | 電池用セパレータおよびその製造方法 |
JP2000007819A (ja) * | 1998-04-21 | 2000-01-11 | Tokuyama Corp | 多孔性フィルムおよびその製造方法 |
JP2000204174A (ja) * | 1999-01-13 | 2000-07-25 | Ube Ind Ltd | 多孔質フイルム及び電池用セパレ―タ |
JP2002151044A (ja) * | 2000-08-30 | 2002-05-24 | Sumitomo Chem Co Ltd | 非水電解液二次電池用セパレータおよび非水電解液二次電池 |
JP2002117825A (ja) * | 2000-10-06 | 2002-04-19 | Denso Corp | 扁平形状巻回型電極体の製造方法 |
JP2005171230A (ja) * | 2003-11-05 | 2005-06-30 | Toray Ind Inc | 二軸配向微多孔フィルムおよびその製造方法 |
JP2009070726A (ja) * | 2007-09-14 | 2009-04-02 | Teijin Ltd | 非水電解質電池の製造方法 |
JP2009238752A (ja) * | 2008-03-27 | 2009-10-15 | Samsung Sdi Co Ltd | 電極組立体及びこれを具備する二次電池 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102569697A (zh) * | 2010-12-29 | 2012-07-11 | 财团法人工业技术研究院 | 隔离膜材及其制备方法以及包含隔离膜的电化学电池 |
JP2012142256A (ja) * | 2010-12-29 | 2012-07-26 | Industrial Technology Research Inst | セパレータ、セパレータを含む電気化学セル、およびセパレータの製造方法 |
JP2014212136A (ja) * | 2010-12-29 | 2014-11-13 | インダストリアル テクノロジー リサーチインスティテュートIndustrial Technology Research Institute | セパレータ、セパレータを含む電気化学セル、およびセパレータの製造方法 |
US9136516B2 (en) | 2010-12-29 | 2015-09-15 | Industrial Technology Research Institute | Hybrid materials using ionic particles |
EP2485297A3 (en) * | 2011-02-03 | 2015-06-03 | Samsung SDI Co., Ltd. | Separator for lithium secondary battery and lithium secondary battery including the same |
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JP2010244875A (ja) | 2010-10-28 |
US20110159347A1 (en) | 2011-06-30 |
KR20110049857A (ko) | 2011-05-12 |
CN102160212A (zh) | 2011-08-17 |
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