WO2011040562A1 - 二次電池用多孔膜及び二次電池 - Google Patents
二次電池用多孔膜及び二次電池 Download PDFInfo
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- H—ELECTRICITY
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- 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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- 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
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/058—Construction or manufacture
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
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- H—ELECTRICITY
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- 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
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- 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
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- 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
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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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- 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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- 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 porous membrane, and more particularly to a porous membrane that is formed on the electrode surface of a lithium ion secondary battery and can contribute to improvement in film uniformity and flexibility and battery cycle characteristics.
- the present invention also relates to a secondary battery electrode provided with such a porous membrane.
- Lithium ion secondary batteries show the highest energy density among practical batteries, and are widely used especially for small electronics. In addition, expansion to automobile applications is also expected, and there is a demand for higher capacity, longer life and further improvement in safety.
- a lithium-ion secondary battery uses a polyolefin-based organic separator such as polyethylene or polypropylene in order to prevent a short circuit between the positive electrode and the negative electrode.
- polyolefin-based organic separators have physical properties that melt at 200 ° C. or lower, volume changes such as shrinkage and melting occur when the battery becomes hot due to internal and / or external stimuli.
- explosion may occur due to short circuit of the negative electrode, release of electric energy, or the like.
- Patent Document 1 polymer particles such as cross-linked polystyrene, cross-linked acrylic resin, and cross-linked fluororesin are used as swellable fine particles whose degree of swelling in an electrolytic solution is increased by heat, and polyethylene is used as heat-fusible fine particles that are melted by heat.
- a porous membrane containing the following polymer particles is disclosed.
- Patent Document 2 discloses polymer particles such as crosslinked styrene resin, crosslinked acrylic resin, and crosslinked fluororesin as swellable fine particles whose degree of swelling in an electrolytic solution is increased by heat, and EVA, ethylene-acrylic as a binder.
- Patent Document 3 discloses a porous film constituted by binding at least two kinds of fine particles including organic fine particles having a melting point of 80 ° C. to 150 ° C. and heat resistant fine particles having a heat resistant temperature of 160 ° C. or higher.
- Patent Document 4 discloses a porous film containing a fibrous material that does not substantially deform at 150 ° C. and organic fine particles having a melting point of 80 to 130 ° C.
- JP 2008-004441 A JP 2008-305783 A (corresponding to US Application Publication No. 2009-67119)
- JP 2006-139978 A JP 2006-164761 A (corresponding to US Application Publication No. 2007-264577)
- an object of the present invention is to provide a porous membrane used for a secondary battery such as a lithium ion secondary battery, which has further improved output characteristics and long-term cycle characteristics as compared with conventional ones.
- the present inventors have combined two kinds of polymer particles having different particle diameters and glass transition temperatures as polymer particles, so that the particle diameter is large and the glass transition temperature is high.
- the polymer particles exhibit porosity, and the polymer particles having a small particle size and a low glass transition temperature act as a binder for binding polymer particles having a large particle size and a high glass transition temperature.
- the effect that low polymer particles show high swelling to the electrolyte is achieved, and as a result, it can have high electrolyte impregnation and electrolyte retention, and in addition to high output characteristics, long-term cycle characteristics are also more As a result, the present invention has been completed.
- the present invention for solving the above-mentioned problems includes the following matters as a gist.
- the polymer particles A having a number average particle size of 0.4 ⁇ m or more and less than 10 ⁇ m and a glass transition point of 65 ° C. or more, and the number average particle size of 0.04 ⁇ m or more and less than 0.3 ⁇ m and having a glass transition point.
- a porous membrane for a secondary battery comprising polymer particles B of 15 ° C. or lower.
- Polymer particles A having a number average particle size of 0.4 ⁇ m or more and less than 10 ⁇ m and a glass transition point of 65 ° C. or more, a number average particle size of 0.04 ⁇ m or more and less than 0.3 ⁇ m, and a glass transition point of 15
- the manufacturing method of the porous film for secondary batteries including the process of apply
- An electrode mixture layer comprising a binder for an electrode mixture layer and an electrode active material is attached to the current collector, and the above (1) to (4) are formed on the surface of the electrode mixture layer.
- the electrode for secondary batteries formed by laminating
- the porous membrane contains specific polymer particles, high electrolyte retention in the porous membrane is achieved, and the output characteristics and long-term cycle characteristics of the obtained secondary battery are further improved.
- the porous membrane for a secondary battery of the present invention has polymer particles A having an average particle size of 0.4 ⁇ m or more and less than 10 ⁇ m and a glass transition point of 65 ° C. or more, and an average particle size of 0.04 ⁇ m or more and less than 0.3 ⁇ m and a glass transition point.
- Polymer particles B of 15 ° C. or lower are included.
- a film having a uniform predetermined thickness can be obtained as a porous film layer, and is included in the inorganic filler Battery performance deterioration due to such impurities can be reduced.
- polymer particles having an average particle size of 0.04 ⁇ m or more and less than 0.3 ⁇ m and a glass transition point of 15 ° C. or less as the polymer particles B, the polymer particles swell into the electrolyte solution, resulting in low internal resistance and output characteristics. , Cycle characteristics are improved.
- the polymer particles A used in the present invention are polymer particles having an average particle size of 0.4 ⁇ m or more and less than 10 ⁇ m and a glass transition point of 65 ° C. or more.
- the average particle diameter of the polymer particles A is less than 0.4 ⁇ m, it is not possible to obtain a film thickness sufficient as the porous film layer, and when the average particle diameter is 10 ⁇ m or more, the porous film layer becomes thick, This will increase the internal resistance.
- the particle size of the polymer particles (polymer particle A, polymer particle B) is a number average particle calculated by measuring the diameter of 100 particle images randomly selected in a transmission electron micrograph and calculating the arithmetic average value thereof. Is the diameter.
- the glass transition temperature of the polymer particles A is 65 ° C. or higher, preferably 75 ° C. or higher, more preferably 85 ° C. or higher.
- the glass transition temperature of the polymer particles A melt at the time of thermal runaway, and the internal resistance increases, thereby obtaining a shutdown effect.
- the glass transition temperature of the polymer particle A is less than 65 ° C., the polymer particle melts at the time of drying, the porosity decreases, and the electrical resistance increases.
- the upper limit of the glass transition temperature of the polymer particles A is 150 ° C.
- the glass transition temperature of a polymer particle (polymer particle A, polymer particle B) can be prepared by combining various monomers. The glass transition temperature of the polymer particles (polymer particle A, polymer particle B) can be measured by DSC.
- Examples of the polymer constituting the polymer particles A include styrene polymers, polymethacrylic acid esters, vinyl polymers, polyethylene, copolymer polyolefins, polyolefin waxes, petroleum waxes, carnauba waxes, and the like. Of these, styrenic polymers, polymethacrylic acid esters, vinyl polymers, and polyethylene are preferred because of the moldability of the polymer particles. Furthermore, polystyrene and polymethacrylic acid ester are preferable because of low swelling property to the electrolytic solution.
- the components constituting the polymer particle A include the following monomers, but are not particularly limited.
- the styrenic polymer is a polymer of an aromatic vinyl monomer such as styrene, or a homopolymer of a styrene derivative, a copolymer of two or more monomers selected from the group consisting of aromatic vinyl and its derivatives. It is a coalescence.
- the content of the aromatic vinyl monomer unit in the styrenic polymer is 60% by mass to 100% by mass, preferably 70% by mass to 100% by mass.
- aromatic vinyl monomers and styrene derivatives include styrene, chlorostyrene, vinyl toluene, t-butyl styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl naphthalene, chloromethyl styrene, hydroxymethyl styrene, ⁇ -methyl styrene, Examples include 2,4-dimethylstyrene and divinylbenzene.
- other copolymerizable monomers can be copolymerized within a range not impairing the effects of the present invention.
- Such copolymer components include diene monomers, olefin monomers, acrylate monomers, fluorine monomers, urethane monomers, silicone monomers, polyamide monomers or polyimide monomers. Examples thereof include a monomer and an ester monomer.
- Polymethacrylate is a homopolymer of methacrylate.
- examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and pentyl methacrylate.
- Examples of the vinyl monomer constituting the vinyl polymer include vinyl alcohol, vinyl acetate, vinyl stearate, and vinyl acetate.
- the number average particle diameter of the polymer particles A is 0.4 ⁇ m or more and less than 10 ⁇ m, preferably 0.8 ⁇ m or more and 6 ⁇ m or less, more preferably 1 ⁇ m or more and 5 ⁇ m or less.
- the polymer particles A can be obtained by a method in which the monomers constituting the polymer particles A in a water-based medium are directly obtained by dispersion polymerization, emulsion polymerization, suspension polymerization, or microsuspension polymerization.
- the content ratio of the polymer particles A in the porous film is preferably 50 to 99% by mass, more preferably 60 to 99% by mass, and most preferably 70 to 99% by mass.
- the content ratio of the polymer particles A in the porous film is in the above range, the effect of increasing the internal resistance due to the melting of the polymer particles A during heating is sufficiently obtained, and the film thickness sufficient as the porous film is maintained. be able to.
- the polymer particles B used in the present invention are polymer particles having a number average particle size of 0.04 ⁇ m or more and less than 0.3 ⁇ m and a glass transition point of 15 ° C. or less.
- a binding point with the polymer particles A can be sufficiently provided, and high binding properties can be expressed. If the number average particle size of the polymer particles B is less than 0.04 ⁇ m, the particles are likely to aggregate, and conversely if the number average particle size is 0.3 ⁇ m or more, the binding point decreases and the binding property decreases.
- the glass transition temperature of the polymer particles B used in the present invention is preferably ⁇ 80 ° C. or higher and 15 ° C. or lower, more preferably ⁇ 75 ° C. or higher and 5 ° C. or lower, and particularly preferably ⁇ 70 ° C. or higher and 0 ° C. or lower.
- flexibility can be given to the porous film at room temperature, and cracking during roll winding and winding, chipping of the porous film layer, and the like can be suppressed. Can do.
- the glass transition temperature of the polymer particles B exceeds 15 ° C., the flexibility of the porous membrane layer is lowered, and cracks at the time of winding and winding, cracking of the porous membrane layer, and the like occur.
- the polymer particles B used in the present invention preferably have a crystallinity of 40% or less and a main chain structure having a saturated structure.
- the degree of crystallinity of the polymer particles B is 40% or less and the main chain structure is a saturated structure, the polymer particles B exhibit swelling property to the electrolytic solution, have excellent oxidation resistance, and can suppress cycle deterioration.
- the degree of crystallinity can be confirmed by X-ray according to JIS K0131. Specifically, the diffraction X-ray intensity from the crystalline portion can be obtained, and the crystallinity can be obtained from the ratio with the total diffraction X-ray intensity (the following formula).
- Xc K ⁇ Ic / It In the above formula, Xc represents the crystallinity of the specimen, Ic represents the diffraction X-ray intensity from the crystalline portion, It represents the entire diffraction X-ray intensity, and K represents the correction term.
- the state in which the main chain structure is a saturated structure means a state in which at least the main chain structure is a saturated bond, and the side chain may be a saturated bond or an unsaturated bond.
- infrared spectroscopy according to JIS K0117 by (IR) refers to a state where there is no peak at 3100cm -1 ⁇ 2900cm -1.
- the polymerization initiator used for the polymerization include lauroyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, 3,3,5-trimethylhexanoyl peroxide, and the like.
- acrylic monomers constituting the polymer particles B acrylic monomers, methacrylic monomers, vinyl ether monomers, epoxy monomers, ester monomers, nitroso monomers, siloxane monomers Monomers, sulfide monomers and the like.
- acrylic monomers, methacrylic monomers, and vinyl ether monomers are preferred, and acrylic monomers are less likely to swell in the electrolyte solution and are less likely to cause bridging and aggregation due to the polymer when dispersed with a small particle size.
- methacrylic monomers are more preferable, and alkyl acrylates or alkyl methacrylates are particularly preferable.
- acrylic monomers examples include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, acrylate-sec-butyl, acrylate-3-pentyl, heptyl acrylate, and hexyl acrylate.
- methacrylic monomers examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, methacrylate-sec-butyl, methacrylate-3-pentyl, heptyl methacrylate, hexyl methacrylate.
- vinyl ether monomers vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl isopropyl ether, vinyl butyl ether, vinyl-sec-butyl ether, vinyl isobutyl ether, vinyl pentyl ether, vinyl hexyl ether, vinyl octyl ether, vinyl Examples include -2-ethylhexyl ether and vinyl methyl thioether.
- Examples of the epoxy monomer include methylene oxide, ethylene oxide, trimethylene oxide, tetraethylene oxide, propylene oxide, ethyl ethylene oxide, butyl ethylene oxide, ethoxymethyl ethylene oxide, allyloxymethyl ethylene oxide, and 2,2-bischloromethyl trimethylene oxide. It is done.
- ester monomers include ethylene adipate, hexamethylene terephthalate, hexamethylene isophthalate, decamethylene isophthalate, adipoyloxydecamethylene, oxy-2-butynyleneoxysebacoyl, dioxyethyleneoxymalonyl, dioxy Ethyleneoxymethylmalonyl, dioxyethyleneoxypentylmalonyl, dioxyethyleneoxysebacoylmalonyl, dioxyethyleneoxyadipoylmalonyl, oxypentamethyleneoxyadipoyl, oxy-2,3-dibromobutadieneoxycarbonyladipoyl Oxy-2,2,3,3,4,4-hexafluoropentamethyleneoxyadipoyl, oxy-1,4-phenyleneisopropylidene-1,4-phenyleneoxysebacoyl .
- nitroso monomer examples include oxytrifluoromethyliminotetrafluoroethylene and oxy-2-bromotetrafluoroethyliminotetrafluoroethylene.
- siloxane monomers include dimethylsiloxane, diethylsiloxane, methylphenylsiloxane, tri (dimethylsiloxane) -1,4-phenylenedimethylsilylene, tetra (dimethylsiloxane) -1,4-phenylenedimethylsilylene, tetra (dimethylsiloxane ) -1,3-phenylenedimethylsilylene, penta (dimethylsiloxane) -1,4-phenylenedimethylsilylene, tri (dimethylsiloxane) oxy (methyl) trimethylsiloxysilylene, tri (dimethylsiloxane) oxy (methyl) -2-phenyl Ethylsilylene, tri (dimethylsiloxane) oxy (methyl) phenylsilylene, tri (dimethylsiloxane) -1,4-phenyleneoxy-1,4-pheny
- sulfide monomers include thiomethylene, thioethylene, dithioethylene, tetrathioethylene, thiotrimethylene, thioisobutylene, thiopropylene, thio-1-ethylethylene, thioneopenylene, thiodifluoromethylene, dithiohexamethylene, dithio
- examples include pentamethylene, dithiodecamethylene, trithiodecamethylene, oxyethylenedithioethylene, oxymethyleneoxyethylenedithioethylene, oxytetramethylenedithiotetramethylene, and thio-1-methyl-3-oxotrimethylene.
- the polymer particle B used in the present invention may contain other components in addition to the above polymerized units of the monomer.
- examples of other components include a monomer containing a hydroxyl group, a monomer containing an N-methylolamide group, a monomer containing an oxetanyl group, and a monomer containing an oxazoline group.
- Esters of polyalkylene glycol and (meth) acrylic acid 2-hydroxyethyl-2 ′ Mono (meth) acrylic esters of dihydroxy esters of dicarboxylic acids such as (meth) acryloyloxyphthalate and 2-hydroxyethyl-2 ′-(meth) acryloyloxysuccinate; 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether Vinyl ethers such as: (meth) allyl-2-hydroxyethyl ether, (meth) allyl-2-hydroxypropyl ether, (meth) allyl-3-hydroxypropyl ether, (meth) allyl-2-hydroxybutyl ether, (meta ) Mono (meth) allyl ethers of alkylene glycols such as allyl-3-hydroxybutyl ether, (meth) allyl-4-hydroxybutyl ether, (meth) allyl-6-hydroxyhexyl ether; Polyoxyalkylene glycol (meth
- Examples of the monomer containing an N-methylolamide group include (meth) acrylamides having a methylol group such as N-methylol (meth) acrylamide.
- Monomers containing an oxetanyl group include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -2-trifluoromethyloxetane, and 3-((meth) acryloyloxymethyl).
- Monomers containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2- Examples thereof include oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like.
- the glass transition temperature of the other components may be 15 ° C. or higher as long as the glass transition temperature of the entire polymer particle B is 15 ° C. or lower.
- the polymer structure such as a monomer or methacrylic monomer is a component exhibiting swelling properties with respect to the electrolyte
- the resulting porous film has higher electrolyte impregnation and electrolyte retention, and the porous film
- the secondary battery having the above is preferable because it exhibits high long-term cycle characteristics.
- the number average particle size of the polymer particles B used in the present invention is 0.04 ⁇ m or more and less than 0.3 ⁇ m, preferably 0.05 ⁇ m or more and 0.2 ⁇ m or less, more preferably 0.05 ⁇ m or more and 0.1 ⁇ m or less.
- the content ratio of the polymer particles B in the porous membrane is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, and most preferably 1 to 30% by mass.
- the content ratio of the polymer particles B in the porous film is in the above range, high swellability to the electrolytic solution is exhibited and flexibility to the porous film can be imparted.
- a dispersant may be used.
- the dispersant used in that case may be those used in ordinary synthesis. Specific examples thereof include benzenesulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylphenylethersulfonate; sodium lauryl sulfate and tetradodecyl.
- Alkyl sulfates such as sodium sulfate; sulfosuccinates such as sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate; fatty acid salts such as sodium laurate; polyoxyethylene lauryl ether sulfate sodium salt, polyoxyethylene nonylphenyl ether sulfate sodium Ethoxy sulfate salts such as salts; alkane sulfonate salts; alkyl ether phosphate sodium salts; polyoxyethylene nonyl phenyl ether, poly Nonionic emulsifiers such as xylethylene sorbitan lauryl ester, polyoxyethylene-polyoxypropylene block copolymer; gelatin, maleic anhydride-styrene copolymer, polyvinylpyrrolidone, sodium polyacrylate, polymerization degree of 700 or more and saponification Examples thereof include water-soluble polymers such
- benzenesulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylphenylethersulfonate
- alkyl sulfates such as sodium lauryl sulfate and sodium tetradodecylsulfate
- oxidation resistance is more preferable.
- it is a benzenesulfonate such as sodium dodecylbenzenesulfonate and sodium dodecylphenylethersulfonate.
- the addition amount of the dispersant can be arbitrarily set, and is usually about 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of monomers.
- the pH when polymer particles A and polymer particles B used in the present invention are dispersed in a dispersion medium is preferably 5 to 13, more preferably 5 to 12, and most preferably 10 to 12.
- the pH is within the above range, so that the storage stability of the binder is improved, and further, the mechanical stability is improved.
- Examples of the pH adjuster for adjusting the pH when the polymer particles A and the polymer particles B are dispersed in the dispersion medium include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, calcium hydroxide, Alkali earth metal oxides such as magnesium hydroxide and barium hydroxide, hydroxides such as hydroxides of metals belonging to Group IIIA in the long periodic table such as aluminum hydroxide; alkali metals such as sodium carbonate and potassium carbonate And carbonates such as carbonates, carbonates such as alkaline earth metal carbonates such as magnesium carbonate, and the like.
- alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide
- calcium hydroxide Alkali earth metal oxides such as magnesium hydroxide and barium hydroxide
- hydroxides such as hydroxides of metals belonging to Group IIIA in the long periodic table such as aluminum hydroxide
- alkali metals such as sodium carbonate and potassium carbonate
- organic amines examples include alkylamines such as ethylamine, diethylamine, and propylamine; monomethanolamine, monoethanolamine, and monopropanol Alcohol amines such as amines; ammonia such as ammonia water Near the like; and the like.
- alkali metal hydroxides are preferable from the viewpoints of binding properties and operability, and sodium hydroxide, potassium hydroxide, and lithium hydroxide are particularly preferable.
- the polymer particles A and polymer particles B used in the present invention are preferably obtained through a particulate metal removal step of removing particulate metals contained in the polymer dispersion in the production process.
- a particulate metal removal step of removing particulate metals contained in the polymer dispersion in the production process.
- the content of the particulate metal component contained in the polymer dispersion is 10 ppm or less, it is possible to prevent metal ion cross-linking over time between polymers in the slurry for a porous film described later, and to prevent an increase in viscosity. Furthermore, there is little concern about self-discharge increase due to internal short circuit of the secondary battery or dissolution / precipitation during charging, and the cycle characteristics and safety of the battery are improved.
- the method for removing the particulate metal component from the polymer solution or polymer dispersion in the particulate metal removal step is not particularly limited.
- Examples thereof include a removal method and a removal method using magnetic force.
- the removal object is a metal component
- the method of removing by magnetic force is preferable.
- the method for removing by magnetic force is not particularly limited as long as it can remove the metal component, but in consideration of productivity and removal efficiency, a magnetic filter is preferably arranged in the production line of polymer particles A and polymer particles B. It is done by doing.
- the mass ratio of the polymer particles A and the polymer particles B in the porous membrane is preferably 99: 1 to 70:30, more preferably 99: 1 to 80:20, and 99: A ratio of 1 to 85:15 is particularly preferable.
- the mass ratio of the polymer particles A and the polymer particles B in the porous film is in the above range, the polymer particles B can be bound to the polymer particles A, and the porosity can be maintained.
- the content ratio of the polymer particles A and the polymer particles B in the porous film is preferably 90% by mass to 5% by mass, and more preferably 80% by mass to 10% by mass.
- the porous film of the present invention may further contain non-conductive particles in addition to the polymer particles A and the polymer particles B as long as the effects of the present invention are not impaired.
- the non-conductive particles those having a melting point of 160 ° C. or higher are preferable.
- the porous film of the present invention further contains non-conductive particles having a melting point of 160 ° C. or higher, even if the separator or the porous film layer melts at a high temperature, the positive electrode and the negative electrode can be prevented from contacting and short-circuiting. it can.
- the non-conductive particles exist stably in a use environment such as a lithium ion secondary battery or a nickel hydride secondary battery, and are electrochemically stable.
- various inorganic particles and organic fibrous materials can be used.
- inorganic particles include oxide particles such as aluminum oxide, boehmite, iron oxide, silicon oxide, magnesium oxide, titanium oxide, BaTiO 2 , ZrO, and alumina-silica composite oxide; nitriding such as aluminum nitride, silicon nitride, and boron nitride Product particles; covalently bonded crystal particles such as silicon and diamond; sparingly soluble ionic crystal particles such as barium sulfate, calcium fluoride and barium fluoride; clay fine particles such as talc and montmorillonite; boehmite, zeolite, apatite, kaolin, mullite, For example, particles derived from mineral resources such as spinel, olivine, sericite, be
- These particles may be subjected to element substitution, surface treatment, solid solution, or the like, if necessary, or may be a single or a combination of two or more.
- oxide particles are preferable from the viewpoints of stability in an electrolytic solution and potential stability.
- the organic fibrous material is not substantially deformed at less than 160 ° C., has an electrical insulating property, is electrochemically stable, and is used as a solvent for an electrolytic solution and a liquid composition described in detail below. There is no particular limitation as long as it is stable.
- the “fibrous material” in the present invention means that having an aspect ratio (length in the longitudinal direction / width (diameter) in a direction perpendicular to the longitudinal direction) of 4 or more.
- Specific constituent materials of the organic fibrous material include, for example, cellulose, modified cellulose (such as carboxymethyl cellulose), polypropylene, polyester (such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate), polyphenylene sulfide, polyaramid, and polyamideimide. And resins such as polyimide.
- polyphenylene sulfide, polyaramid, polyamideimide, and polyimide are preferable from the viewpoints of stability in an electrolytic solution and potential stability.
- the organic fibrous material may contain one kind of these constituent materials, or may contain two or more kinds. Further, the organic fibrous material may contain, as necessary, various known additives (for example, an antioxidant in the case of a resin) in addition to the above-described constituent materials. I do not care.
- the shape of the non-conductive particles may be, for example, a so-called spherical shape, a plate shape, or a needle shape. More preferably, it is a plate-like particle. In the case where the non-conductive particles are plate-like, it can be expected to further improve the effect of preventing a short circuit due to lithium dendrite.
- the aspect ratio is preferably 5 or more, more preferably 5 or more and 1000 or less, further preferably 7 or more and 800 or less, and 9 or more and 600 or less. Is particularly preferred.
- the average value of the ratio of the major axis direction length to the minor axis direction length of the flat plate surface is 0.3 or more, more preferably 0.5 or more. 3 or less, more preferably 2 or less.
- non-electrically conductive material such as carbon black, graphite, SnO 2 , ITO, metal powder and fine powders of conductive compounds and oxides
- electrical insulation is achieved. It is also possible to use it with a certain character.
- non-electrically conductive particles may be used in combination of two or more.
- non-conductive particles having a foreign metal content of 100 ppm or less it is preferable to use non-conductive particles having a foreign metal content of 100 ppm or less.
- the metal foreign matter or metal ion is eluted, which causes ionic crosslinking with the polymer in the slurry for porous film, There is a possibility that the slurry for the porous film aggregates and as a result, the porosity of the porous film decreases and the output characteristics deteriorate.
- the metal it is most preferable to contain Fe, Ni, Cr and the like which are particularly easily ionized.
- the metal content in the non-conductive particles is preferably 100 ppm or less, more preferably 50 ppm or less.
- the term “metal foreign matter” as used herein means a simple metal other than non-conductive particles.
- the content of the metal foreign matter in the non-conductive particles can be measured using ICP (Inductively Coupled Plasma).
- the average particle diameter (volume average D50 average particle diameter) of the non-conductive particles is preferably 5 nm to 10 ⁇ m, more preferably 10 nm to 5 ⁇ m.
- the average particle diameter of the non-conductive particles be in the range of 50 nm or more and 2 ⁇ m or less because the dispersion, the ease of coating, and the controllability of voids are excellent.
- the BET specific surface area of these particles is specifically 0.9 to 200 m 2 / g from the viewpoint of suppressing the aggregation of the particles and optimizing the fluidity of the slurry for a porous film described later. Preferably, it is 1.5 to 150 m 2 / g.
- the content of non-conductive particles in the porous membrane is preferably 5% by mass to 95% by mass, more preferably 20% by mass to 90% by mass.
- the porous membrane may further include a dispersant, a leveling agent, an antioxidant, a binder for the porous membrane, a thickener, an electrolytic solution additive having a function of inhibiting decomposition of the electrolytic solution, etc. May be included. These are not particularly limited as long as they do not affect the battery reaction.
- dispersant examples include anionic compounds, cationic compounds, nonionic compounds, and polymer compounds.
- a dispersing agent is selected according to the nonelectroconductive particle to be used.
- the content ratio of the dispersant in the porous film is preferably within a range that does not affect the battery characteristics, and specifically 10 mass% or less.
- leveling agent examples include surfactants such as alkyl surfactants, silicon surfactants, fluorine surfactants, and metal surfactants. By mixing the surfactant, it is possible to prevent the repelling that occurs during coating or to improve the smoothness of the electrode.
- antioxidants examples include a phenol compound, a hydroquinone compound, an organic phosphorus compound, a sulfur compound, a phenylenediamine compound, and a polymer type phenol compound.
- the polymer type phenol compound is a polymer having a phenol structure in the molecule, and a polymer type phenol compound having a weight average molecular weight of 200 to 1000, preferably 600 to 700 is preferably used.
- a binder for a porous film polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyacrylic acid derivatives, polyacrylonitrile derivatives, soft polymers, etc. used in the electrode mixture layer binder described later Can be used.
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- polyacrylic acid derivatives polyacrylonitrile derivatives
- soft polymers etc. used in the electrode mixture layer binder described later Can be used.
- thickeners include cellulose polymers such as carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, and ammonium salts and alkali metal salts thereof; (modified) poly (meth) acrylic acid and ammonium salts and alkali metal salts thereof; ) Polyvinyl alcohols such as polyvinyl alcohol, copolymers of acrylic acid or acrylate and vinyl alcohol, maleic anhydride or copolymers of maleic acid or fumaric acid and vinyl alcohol; polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, modified Polyacrylic acid, oxidized starch, phosphoric acid starch, casein, various modified starches, acrylonitrile-butadiene copolymer hydride, and the like.
- cellulose polymers such as carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, and ammonium salts and alkali metal salts thereof; (modified) poly (meth) acrylic acid and ammonium salts and alkali metal salts thereof
- (modified) poly means “unmodified poly” or “modified poly”
- (meth) acryl means “acryl” or “methacryl”.
- vinylene carbonate used in the electrode mixture layer slurry and the electrolytic solution described later can be used.
- Other examples include nanoparticles such as fumed silica and fumed alumina, and surfactants such as alkyl surfactants, silicon surfactants, fluorine surfactants, and metal surfactants.
- the content ratio of the other components in the porous film is preferably in a range that does not affect the battery characteristics. Specifically, each component is 10% by mass or less, and the total content of other components is 20% by mass or less. .
- Method for producing porous membrane As a method for producing the porous membrane of the present invention, 1) a method of applying a slurry for a porous membrane containing polymer particles A, polymer particles B and a solvent on a predetermined substrate and then drying; 2) polymer particles A, A method of immersing a substrate in a slurry for a porous membrane containing polymer particles B and a solvent and then drying the substrate; 3) applying a slurry for a porous membrane containing polymer particles A, polymer particles B and a solvent on a release film; A method of drying and transferring the obtained porous film onto a predetermined substrate.
- 1) The method of applying the slurry for the porous film containing the polymer particles A, the polymer particles B and the solvent to the substrate and then drying is most preferable because the film thickness of the porous film can be easily controlled.
- the porous membrane production method of the present invention is characterized in that the porous membrane slurry is applied to a substrate and then dried.
- the slurry for a porous membrane of the present invention comprises polymer particles A, polymer particles B, and a solvent.
- the polymer particle A and the polymer particle B those described for the porous film are used.
- the solvent is not particularly limited as long as it can uniformly disperse the solid content (polymer particles A, polymer particles B and other components).
- the solvent used for the slurry for the porous membrane either water or an organic solvent can be used.
- organic solvents include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; ketones such as acetone, ethylmethylketone, diisopropylketone, cyclohexanone, methylcyclohexane, and ethylcyclohexane.
- Chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, ⁇ -butyrolactone and ⁇ -caprolactone; Acylonitriles such as acetonitrile and propionitrile; Tetrahydrofuran and Ethylene Ethers such as glycol diethyl ether; alcohols such as methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether; N-methyl Amides such as pyrrolidone and N, N-dimethylformamide are exemplified. These solvents may be used alone, or two or more of these may be mixed and used as a mixed solvent. Among these, water is particularly preferable because of low solubility of the polymer.
- the solid content concentration of the slurry for the porous membrane is not particularly limited as long as it can be applied and immersed and has a fluid viscosity, but is generally about 10 to 50% by mass.
- the slurry for the porous film further includes other components such as non-conductive particles, a dispersant, and an electrolytic solution additive having a function of inhibiting decomposition of the electrolytic solution. It may be included. These are not particularly limited as long as they do not affect the battery reaction.
- the manufacturing method of the slurry for porous films is not particularly limited, and can be obtained by mixing the polymer particles A, the polymer particles B, and the solvent and other components added as necessary.
- a porous film slurry in which polymer particles A and polymer particles B are highly dispersed can be obtained regardless of the mixing method and mixing order by using the above components.
- the mixing device is not particularly limited as long as it can uniformly mix the above components, and a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, and the like can be used.
- the viscosity of the slurry for the porous membrane is preferably 10 mPa ⁇ s to 10,000 mPa ⁇ s, more preferably 50 to 500 mPa ⁇ s, from the viewpoints of uniform coatability and slurry aging stability.
- the viscosity is a value measured using a B-type viscometer at 25 ° C. and a rotation speed of 60 rpm.
- the substrate is not particularly limited, but the porous membrane of the present invention is particularly preferably formed on an electrode for a secondary battery or an organic separator. Among these, it is more preferable to form on the electrode surface for secondary batteries.
- the porous film of the present invention By forming the porous film of the present invention on the electrode surface, high safety is maintained without causing a short circuit between the positive electrode and the negative electrode even when the organic separator shrinks due to heat.
- the porous film of the present invention can function as a separator without an organic separator, and a battery can be manufactured at low cost.
- the porous membrane of the present invention is formed on a substrate other than an electrode or an organic separator, it is used by peeling the porous membrane from the substrate and directly laminating it on the electrode or the organic separator when assembling the battery. be able to.
- the method for applying the slurry for the porous film onto the substrate is not particularly limited. Examples thereof include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method. Among them, the dip method and the gravure method are preferable in that a uniform porous film can be obtained.
- the drying method include drying by warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams. The drying temperature can be changed depending on the type of solvent used.
- a low-volatility solvent such as N-methylpyrrolidone
- it is preferably dried at a high temperature of 120 ° C. or higher with a blower-type dryer.
- a highly volatile solvent when used, it can be dried at a low temperature of 100 ° C. or lower.
- drying at a low temperature of 100 ° C. or lower is preferable.
- the adhesion between the electrode mixture layer and the porous film can be improved by a press treatment using a mold press or a roll press.
- the pressure treatment is excessively performed, the porosity of the porous film may be impaired, so the pressure and the pressure time are controlled appropriately.
- the film thickness of the porous film is not particularly limited and is appropriately set according to the use or application field of the porous film. However, if the film is too thin, a uniform film cannot be formed. Since the capacity per volume (mass) decreases, 0.5 to 50 ⁇ m is preferable, and 0.5 to 10 ⁇ m is more preferable.
- the porous membrane of the present invention is formed on the surface of the electrode mixture layer or organic separator of the secondary battery electrode, and is particularly preferably used as a protective film or separator for the electrode mixture layer.
- the secondary battery electrode on which the porous film is formed is not particularly limited, and the porous film of the present invention can be formed on electrodes having various configurations.
- the porous film may be formed on any surface of the positive electrode and the negative electrode of the secondary battery, or may be formed on both the positive electrode and the negative electrode.
- the electrode mixture layer containing the electrode mixture layer binder and the electrode active material is attached to the current collector, and on the surface of the electrode mixture layer, The porous film is laminated.
- Electrode active material What is necessary is just to select the electrode active material used for the electrode for secondary batteries of this invention according to the secondary battery in which an electrode is utilized.
- the secondary battery include a lithium ion secondary battery and a nickel hydride secondary battery.
- the electrode active material (positive electrode active material) for the lithium ion secondary battery positive electrode is composed of an inorganic compound and an organic compound. It is roughly divided into Examples of the positive electrode active material made of an inorganic compound include transition metal oxides, composite oxides of lithium and transition metals, and transition metal sulfides. As the transition metal, Fe, Co, Ni, Mn and the like are used.
- the inorganic compound used for the positive electrode active material include LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiFePO 4 , LiFeVO 4 and other lithium-containing composite metal oxides; TiS 2 , TiS 3 , non- Transition metal sulfides such as crystalline MoS 2 ; transition metal oxides such as Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , MoO 3 , V 2 O 5 , V 6 O 13 It is done. These compounds may be partially element-substituted.
- the positive electrode active material made of an organic compound for example, a conductive polymer such as polyacetylene or poly-p-phenylene can be used.
- An iron-based oxide having poor electrical conductivity may be used as an electrode active material covered with a carbon material by allowing a carbon source material to be present during reduction firing. These compounds may be partially element-substituted.
- the positive electrode active material for a lithium ion secondary battery may be a mixture of the above inorganic compound and organic compound.
- the particle diameter of the positive electrode active material is appropriately selected in consideration of other constituent elements of the battery. From the viewpoint of improving battery characteristics such as output characteristics and cycle characteristics, the 50% volume cumulative diameter is usually 0.1. It is ⁇ 50 ⁇ m, preferably 1 to 20 ⁇ m. When the 50% volume cumulative diameter is within this range, a secondary battery having a large charge / discharge capacity can be obtained, and handling of the slurry for electrodes and the electrodes is easy.
- the 50% volume cumulative diameter can be determined by measuring the particle size distribution by laser diffraction.
- examples of the electrode active material (negative electrode active material) for the lithium ion secondary battery negative electrode include amorphous carbon, graphite, natural graphite, Examples thereof include carbonaceous materials such as mesocarbon microbeads and pitch-based carbon fibers, and conductive polymers such as polyacene.
- the negative electrode active material metals such as silicon, tin, zinc, manganese, iron, nickel, alloys thereof, oxides or sulfates of the metals or alloys are used.
- lithium alloys such as lithium metal, Li—Al, Li—Bi—Cd, and Li—Sn—Cd, lithium transition metal nitride, silicon, and the like can be used.
- the electrode active material a material obtained by attaching a conductivity imparting material to the surface by a mechanical modification method can also be used.
- the particle size of the negative electrode active material is appropriately selected in consideration of the other structural requirements of the battery. From the viewpoint of improving battery characteristics such as initial efficiency, output characteristics, and cycle characteristics, a 50% volume cumulative diameter is usually The thickness is 1 to 50 ⁇ m, preferably 15 to 30 ⁇ m.
- nickel hydroxide particles may be mentioned as an electrode active material (positive electrode active material) for a nickel metal hydride secondary battery positive electrode.
- the nickel hydroxide particles may be dissolved in cobalt, zinc, cadmium, or the like, or may be coated with a cobalt compound whose surface is subjected to an alkali heat treatment.
- nickel hydroxide particles include cobalt compounds such as cobalt oxide, metal cobalt and cobalt hydroxide, zinc compounds such as metal zinc, zinc oxide and zinc hydroxide, and rare earth compounds such as erbium oxide.
- the additive may be contained.
- the hydrogen storage alloy particles are used when charging the battery.
- an electrode active material negative electrode active material
- the hydrogen storage alloy particles are used when charging the battery.
- the hydrogen storage alloy particles are preferred. Specifically, for example, LaNi 5 , MmNi 5 (Mm is a misch metal), LmNi 5 (Lm is at least one selected from rare earth elements including La), and a part of Ni of these alloys is Al, Mn, Co.
- hydrogen storage alloy particles having a composition represented by the general formula: LmNiwCoxMnyAlz (the total value of atomic ratios w, x, y, z is 4.80 ⁇ w + x + y + z ⁇ 5.40) This is suitable because the pulverization associated with is suppressed and the charge / discharge cycle life is improved.
- an electrode mixture layer contains the binder for electrode mixture layers other than an electrode active material.
- the binder for the electrode By including the binder for the electrode, the binding property of the electrode mixture layer in the electrode is improved, the strength against the mechanical force applied during the process such as winding of the electrode is increased, and the electrode combination in the electrode is increased. Since the agent layer is less likely to be detached, the risk of a short circuit due to the desorbed material is reduced.
- various resin components can be used.
- polyethylene polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivatives, polyacrylonitrile derivatives, and the like can be used. These may be used alone or in combination of two or more.
- the soft polymer illustrated below can also be used as a binder for electrode mixture layers.
- Acrylic acid such as polybutyl acrylate, polybutyl methacrylate, polyhydroxyethyl methacrylate, polyacrylamide, polyacrylonitrile, butyl acrylate / styrene copolymer, butyl acrylate / acrylonitrile copolymer, butyl acrylate / acrylonitrile / glycidyl methacrylate copolymer
- Isobutylene-based soft polymers such as polyisobutylene, isobutylene-isoprene rubber, isobutylene-styrene copolymer;
- Olefinic soft polymers of Vinyl-based soft polymers such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinyl acetate / styrene copolymer; Epoxy-based soft polymers such as polyethylene oxide, polypropylene oxide, epichlorohydrin rubber; Fluorine-containing soft polymers such as vinylidene fluoride rubber and tetrafluoroethylene-propylene rubber; Examples thereof include other soft polymers such as natural rubber, polypeptide, protein, polyester-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, and polyamide-based thermoplastic elastomer. These soft polymers may have a cross-linked structure or may have a functional group introduced by modification.
- the amount of the binder for the electrode mixture layer in the electrode mixture layer is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, particularly preferably 100 parts by mass of the electrode active material. Is 0.5 to 3 parts by mass. When the amount of the binder for the electrode mixture layer is within the above range, it is possible to prevent the active material from dropping from the electrode without inhibiting the battery reaction.
- the binder for the electrode mixture layer is prepared as a solution or a dispersion to produce an electrode.
- the viscosity at that time is usually in the range of 1 mPa ⁇ s to 300,000 mPa ⁇ s, preferably 50 mPa ⁇ s to 10,000 mPa ⁇ s.
- the viscosity is a value measured using a B-type viscometer at 25 ° C. and a rotation speed of 60 rpm.
- the electrode mixture layer may contain a conductivity imparting material or a reinforcing material.
- a conductivity imparting material conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor-grown carbon fiber, and carbon nanotube can be used. Examples thereof include carbon powders such as graphite, and fibers and foils of various metals.
- the reinforcing material various inorganic and organic spherical, plate-like, rod-like or fibrous fillers can be used.
- the amount of the conductivity-imparting material and the reinforcing agent used is usually 0 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the electrode active material.
- the electrode mixture layer is obtained by attaching a slurry containing an electrode mixture layer binder, an electrode active material, and a solvent (hereinafter sometimes referred to as “electrode mixture layer forming slurry”) to a current collector. Can be formed.
- any solvent may be used as long as it dissolves or disperses the binder for electrode mixture layer in the form of particles.
- the electrode active layer binder is adsorbed on the surface, thereby stabilizing the dispersion of the electrode active material and the like.
- the solvent used for the electrode mixture layer forming slurry either water or an organic solvent can be used.
- the organic solvent include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; ketones such as ethyl methyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ⁇ -butyrolactone, ⁇ -Esters such as caprolactone; acylonitriles such as acetonitrile and propionitrile; ethers such as tetrahydrofuran and ethylene glycol diethyl ether; alcohols such as methanol, ethanol, isopropanol, ethylene glycol and ethylene glycol monomethyl ether; N-methyl Amides such as pyrrolidone and N, N-dimethylformamide are exemplified. These solvents may be used alone or in admix
- the electrode mixture layer forming slurry may contain a thickener.
- a polymer soluble in the solvent used for the slurry for forming the electrode mixture layer is used.
- the thickener the thickener exemplified in the porous film of the present invention can be used.
- the amount of the thickener used is preferably 0.5 to 1.5 parts by mass with respect to 100 parts by mass of the electrode active material. When the use amount of the thickener is within this range, the coating property and the adhesion with the current collector are good.
- the electrode mixture layer forming slurry contains trifluoropropylene carbonate, vinylene carbonate, catechol carbonate, 1,6-dioxaspiro [4,4] nonane in order to increase the stability and life of the battery.
- -2,7-dione, 12-crown-4-ether and the like can be used. These may be used by being contained in an electrolyte solution described later.
- the amount of the solvent in the electrode mixture layer forming slurry is adjusted so as to have a viscosity suitable for coating depending on the type of the electrode active material, the electrode mixture layer binder and the like.
- the solid content concentration of the electrode active material, the binder for the electrode mixture layer, and other additives is preferably 30. It is used by adjusting the amount to ⁇ 90 mass%, more preferably 40 to 80 mass%.
- the slurry for forming the electrode mixture layer is prepared by mixing an electrode active material, a binder for the electrode mixture layer, other additives such as a conductivity-imparting material added as necessary, and a solvent using a mixer. Obtained. Mixing may be performed by supplying the above components all at once to a mixer. When the electrode active material, the electrode mixture layer binder, the conductivity-imparting material and the thickener are used as the constituents of the electrode mixture layer-forming slurry, the conductivity-imparting material and the thickener are contained in the solvent.
- the conductivity-imparting material is dispersed in the form of fine particles, and then the electrode mixture layer binder and the electrode active material are added and further mixed, since the dispersibility of the resulting slurry can be improved.
- a ball mill, sand mill, pigment disperser, crusher, ultrasonic disperser, homogenizer, planetary mixer, Hobart mixer, etc. can be used. It is preferable because aggregation of the resin can be suppressed.
- the particle size of the electrode mixture layer forming slurry is preferably 35 ⁇ m or less, and more preferably 25 ⁇ m or less.
- the conductive material is highly dispersible and a homogeneous electrode can be obtained.
- the current collector is not particularly limited as long as it is an electrically conductive and electrochemically durable material. From the viewpoint of having heat resistance, for example, iron, copper, aluminum, nickel, stainless steel, etc. Metal materials such as titanium, tantalum, gold, and platinum are preferable. Among these, aluminum is particularly preferable for the positive electrode of the lithium ion secondary battery, and copper is particularly preferable for the negative electrode of the lithium ion secondary battery.
- the shape of the current collector is not particularly limited, but a sheet shape having a thickness of about 0.001 to 0.5 mm is preferable. In order to increase the adhesive strength of the electrode mixture layer, the current collector is preferably used after being roughened.
- Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.
- a mechanical polishing method an abrasive cloth paper with a fixed abrasive particle, a grindstone, an emery buff, a wire brush provided with a steel wire or the like is used.
- an intermediate layer may be formed on the current collector surface in order to increase the adhesive strength and conductivity of the electrode mixture layer.
- the method for producing the electrode mixture layer may be any method in which the electrode mixture layer is bound in layers on at least one side, preferably both sides of the current collector.
- the electrode mixture layer forming slurry is applied to a current collector, dried, and then heated at 120 ° C. or higher for 1 hour or longer to form an electrode mixture layer.
- the method for applying the electrode mixture layer forming slurry to the current collector is not particularly limited. Examples thereof include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method.
- the drying method include drying by warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams.
- the porosity of the electrode mixture layer of the electrode is preferably cured.
- the thickness of the electrode mixture layer is usually 5 to 300 ⁇ m, preferably 10 to 250 ⁇ m, for both the positive electrode and the negative electrode.
- the separator for a secondary battery of the present invention is formed by laminating the porous film on an organic separator.
- organic separator As an organic separator, well-known things, such as a separator containing polyolefin resin, such as polyethylene and a polypropylene, and an aromatic polyamide resin, are used. As the organic separator used in the present invention, a porous membrane having a fine pore size, having no electron conductivity and ionic conductivity and high resistance to organic solvents is used.
- the thickness of the entire separator can be reduced, the active material ratio in the battery can be increased, and the capacity per volume can be increased.
- a microporous membrane is preferred.
- the thickness of the organic separator is usually 0.5 to 40 ⁇ m, preferably 1 to 30 ⁇ m, more preferably 1 to 10 ⁇ m. Within this range, resistance due to the separator in the battery is reduced, and workability at the time of coating on the organic separator is good.
- examples of the polyolefin-based resin used as the material for the organic separator include homopolymers such as polyethylene and polypropylene, copolymers, and mixtures thereof.
- examples of the polyethylene include low density, medium density, and high density polyethylene, and high density polyethylene is preferable from the viewpoint of piercing strength and mechanical strength. These polyethylenes may be mixed in two or more types for the purpose of imparting flexibility.
- the polymerization catalyst used for these polyethylenes is not particularly limited, and examples thereof include Ziegler-Natta catalysts, Phillips catalysts, and metallocene catalysts.
- the viscosity average molecular weight of polyethylene is preferably 100,000 or more and 12 million or less, more preferably 200,000 or more and 3 million or less.
- polypropylene include homopolymers, random copolymers, and block copolymers, and one kind or a mixture of two or more kinds can be used.
- the polymerization catalyst is not particularly limited, and examples thereof include Ziegler-Natta catalysts and metallocene catalysts.
- the stereoregularity is not particularly limited, and isotactic, syndiotactic or atactic can be used. However, it is desirable to use isotactic polypropylene because it is inexpensive.
- an appropriate amount of a polyolefin other than polyethylene or polypropylene, and an additive such as an antioxidant or a nucleating agent may be added to the polyolefin as long as the effects of the present invention are not impaired.
- a publicly known one is used. For example, after polypropylene and polyethylene are melt-extruded to form a film, annealing is performed at a low temperature to grow a crystal domain, and stretching is performed in this state.
- a wet method in which a microporous film is formed by removing a film that has started to form a gathered island phase by using this solvent or other low-molecular solvent with another volatile solvent is selected.
- a dry method is preferable in that a large void can be easily obtained for the purpose of reducing the resistance.
- the organic separator used in the present invention may contain other fillers and fiber compounds for the purpose of controlling strength, hardness, and heat shrinkage.
- it when laminating the porous film, it may be coated with a low molecular weight compound or a high molecular compound in advance for the purpose of improving the adhesion or improving the liquid impregnation property by lowering the surface tension with the electrolytic solution.
- electromagnetic radiation treatment such as ultraviolet rays, plasma treatment such as corona discharge and plasma gas may be performed.
- the coating treatment is preferably performed with a polymer compound containing a polar group such as a carboxylic acid group, a hydroxyl group, and a sulfonic acid group from the viewpoint that the impregnation property of the electrolytic solution is high and the adhesion with the porous film is easily obtained.
- a polar group such as a carboxylic acid group, a hydroxyl group, and a sulfonic acid group
- the secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolyte solution, and the porous film is laminated on at least one of the positive electrode, the negative electrode, and the separator.
- Examples of the secondary battery include a lithium ion secondary battery and a nickel hydride secondary battery.
- improvement of safety is most demanded and the effect of introducing a porous film is the highest, and in addition, improvement of output characteristics is cited as an issue. Therefore, a lithium ion secondary battery is preferable.
- the case where it uses for a lithium ion secondary battery is demonstrated.
- Electrode As the electrolytic solution for the lithium ion secondary battery, an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is used. A lithium salt is used as the supporting electrolyte.
- the lithium salt is not particularly limited, LiPF 6, LiAsF 6, LiBF 4, LiSbF 6, LiAlCl 4, LiClO 4, CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi, (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like.
- LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferable. Two or more of these may be used in combination. Since the lithium ion conductivity increases as the supporting electrolyte having a higher degree of dissociation is used, the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
- the organic solvent used in the electrolyte for the lithium ion secondary battery is not particularly limited as long as it can dissolve the supporting electrolyte, but dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene Carbonates such as carbonate (PC), butylene carbonate (BC) and methyl ethyl carbonate (MEC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfolane and dimethyl sulfoxide Sulfur-containing compounds such as are preferably used. Moreover, you may use the liquid mixture of these solvents.
- DMC dimethyl carbonate
- EC ethylene carbonate
- DEC diethyl carbonate
- PC butylene carbonate
- MEC methyl ethyl carbonate
- esters such as ⁇ -butyrolactone and methyl formate
- ethers such as 1,2-d
- carbonates are preferable because they have a high dielectric constant and a wide stable potential region. Since the lithium ion conductivity increases as the viscosity of the solvent used decreases, the lithium ion conductivity can be adjusted depending on the type of the solvent. Moreover, it is also possible to use the electrolyte solution by containing an additive. Examples of the additive include carbonate compounds such as vinylene carbonate (VC) used in the electrode mixture layer slurry.
- VC vinylene carbonate
- the concentration of the supporting electrolyte in the electrolytic solution for the lithium ion secondary battery is usually 1 to 30% by mass, preferably 5 to 20% by mass.
- the concentration is usually 0.5 to 2.5 mol / L depending on the type of the supporting electrolyte. If the concentration of the supporting electrolyte is too low or too high, the ionic conductivity tends to decrease. Since the degree of swelling of the polymer particles increases as the concentration of the electrolytic solution used decreases, the lithium ion conductivity can be adjusted by the concentration of the electrolytic solution.
- electrolytic solution other than the above examples include polymer electrolytes such as polyethylene oxide and polyacrylonitrile, gelled polymer electrolytes in which the polymer electrolyte is impregnated with an electrolytic solution, and inorganic solid electrolytes such as LiI and Li 3 N.
- the organic separator illustrated by the above-mentioned separator for secondary batteries is mentioned.
- the positive electrode and the negative electrode include those in which an electrode mixture layer including an electrode mixture layer binder and an electrode active material exemplified in the secondary battery electrode is attached to a current collector.
- the positive electrode or the negative electrode in which the porous film is laminated may be used as the positive electrode or the negative electrode, and the separator in which the porous film is laminated may be the secondary battery.
- a battery separator may be used as the separator.
- a positive electrode and a negative electrode are overlapped via a separator, and this is wound into a battery container according to the shape of the battery.
- the method of injecting and sealing is mentioned.
- the porous film of the present invention is formed on either the positive electrode, the negative electrode, or the separator. In addition, lamination with only a porous film is possible. If necessary, an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate, or the like can be inserted to prevent an increase in pressure inside the battery and overcharge / discharge.
- the shape of the battery may be any of a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like.
- Example Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
- the part and% in a present Example are a mass reference
- various physical properties are evaluated as follows.
- the capacity retention represented by the ratio (b / a (%)) of the electric capacity of 5C, 10C, 20C discharge capacity b and 0.1C discharge capacity a is obtained, and this is used as an evaluation standard for output characteristics. Judgment by The higher this value, the better the output characteristics.
- SA 60% or more A: 50% or more and less than 60%
- B 30% or more and less than 50%
- C 10% or more and less than 30%
- D 1% or more and less than 10%
- E less than 1%
- ⁇ Battery characteristics cycle characteristics> Using the obtained coin-type lithium ion secondary battery, charging was performed from 3 V to 4.3 V at 0.1 C and then from 4.3 V to 3 V at 0.1 C at 25 ° C. and 60 ° C., respectively. The discharge is repeated 100 cycles, and the value obtained by calculating the percentage of the 0.1C discharge capacity at the 100th cycle with respect to the 0.1C discharge capacity at the 5th cycle as a percentage is determined as the following criteria. The larger this value, the less the discharge capacity decreases, and the longer-term cycle characteristics are better.
- SA 80% or more A: 70% or more and less than 80% B: 60% or more and less than 70% C: 50% or more and less than 60% D: 40% or more and less than 50% E: 30% or more and less than 40% F: less than 30%
- Example 1 As the polymer particles A-1, polystyrene particles having a number average particle diameter of 3 ⁇ m and a glass transition temperature of 100 ° C. (PP-30-10 manufactured by Spherotech) were used.
- the obtained polymer particle B-1 had a glass transition temperature of ⁇ 55 ° C. and a number average particle diameter of 0.1 ⁇ m. Further, the crystallinity of the polymer particle B-1 was 40% or less, and the main chain structure was a saturated structure.
- PVDF polyvinylidene fluoride
- Electrode composition for positive electrode and positive electrode 92 parts of lithium manganate having a spinel structure as a positive electrode active material, 5 parts of acetylene black, and 3 parts of PVDF (polyvinylidene fluoride) as a binder for the electrode mixture layer are added in solid content, and solid with NMP. After adjusting the concentration to 87%, the mixture was mixed for 60 minutes with a planetary mixer. Further, the solid content concentration was adjusted to 84% with NMP, and then mixed for 10 minutes to prepare a slurry-like electrode composition for positive electrode (slurry for forming a positive electrode mixture layer). This positive electrode composition was applied to an aluminum foil having a thickness of 18 ⁇ m, dried at 120 ° C. for 3 hours, and then roll-pressed to obtain a positive electrode having a positive electrode mixture layer having a thickness of 50 ⁇ m.
- PVDF polyvinylidene fluoride
- a single-layer polypropylene separator (porosity 55%) produced by a dry method having a diameter of 13 mm, a porous membrane-attached negative electrode 1 having a diameter of 14 mm, and a thickness of 25 ⁇ m was cut into a circle having a diameter of 18 mm.
- a negative electrode with a porous film is disposed on the positive electrode mixture layer surface side of the positive electrode so that the electrode mixture layers face each other and the positive electrode aluminum foil is in contact with the bottom surface of the outer container, and further the negative electrode copper foil
- the battery can was sealed, and a full-cell coin cell having a diameter of 20 mm and a thickness of about 3.2 mm was manufactured (coin cell CR2032). The obtained battery was measured for output characteristics and cycle characteristics. The results are shown in Table 1.
- Example 2 As the polymer particles A, polystyrene particles having a glass transition temperature of 100 ° C. and a number average particle diameter of 7 ⁇ m (manufactured by Spherotech, PP-60-10, hereinafter sometimes referred to as “polymer particles A-2”) are used. Except for the above, in the same manner as in Example 1, a slurry for a porous film, an electrode with a porous film, and a coin-type lithium ion secondary battery were obtained, and output characteristics and cycle characteristics were measured. The results are shown in Table 1.
- polystyrene particles having a glass transition temperature of 100 ° C. and a number average particle size of 0.5 ⁇ m manufactured by Spherotech, PP-05-10, hereinafter sometimes referred to as “polymer particles A-3”. Except for the use, in the same manner as in Example 1, a slurry for a porous membrane, an electrode with a porous membrane, and a coin-type lithium ion secondary battery were obtained, and output characteristics and cycle characteristics were measured. The results are shown in Table 2.
- Example 4 ⁇ Production of polymer particle B-2> To Polymerization Can A, 12 parts of n-butyl acrylate, 0.12 part of sodium lauryl sulfate and 79 parts of ion-exchanged water were added, 0.2 part of ammonium persulfate and 10 parts of ion-exchanged water were added as a polymerization initiator, and the mixture was heated to 60 ° C. After warming and stirring for 90 minutes, an emulsion prepared by adding 88 parts of n-butyl acrylate, 0.3 part of sodium lauryl sulfate, and 46 parts of ion-exchanged water to another polymerization vessel B is polymerized over about 180 minutes.
- the obtained polymer particle B-2 had a glass transition temperature of ⁇ 55 ° C. and a number average particle diameter of 0.3 ⁇ m. Further, the crystallinity of the polymer particle B-2 was 40% or less, and the main chain structure was a saturated structure.
- a slurry for a porous membrane, an electrode with a porous membrane, and a coin-type lithium ion secondary battery were obtained in the same manner as in Example 1 except that the polymer particle B-2 was used as the polymer particle B, and the output characteristics were obtained. And the cycle characteristics were measured. The results are shown in Table 2.
- Example 5 ⁇ Production of polymer particle B-3> To Polymerization Can A, 12 parts of n-butyl acrylate, 0.12 part of sodium lauryl sulfate and 79 parts of ion-exchanged water were added, 0.2 part of ammonium persulfate and 10 parts of ion-exchanged water were added as a polymerization initiator, and the mixture was heated to 60 ° C. After warming and stirring for 90 minutes, an emulsion prepared by adding 88 parts of n-butyl acrylate, 2.7 parts of sodium lauryl sulfate, and 46 parts of ion-exchanged water to another polymerization vessel B was polymerized over about 180 minutes.
- the obtained polymer particle B-3 had a glass transition temperature of ⁇ 55 ° C. and a number average particle diameter of 0.05 ⁇ m. Further, the crystallinity of the polymer particle B-3 was 40% or less, and the main chain structure was a saturated structure.
- polymer particles A polymethyl methacrylate particles having a glass transition temperature of 70 ° C. and a number average particle diameter of 3 ⁇ m (MX-300, manufactured by Soken Chemical Co., Ltd., hereinafter sometimes referred to as “polymer particles A-4”) Except that was used, a slurry for a porous membrane, an electrode with a porous membrane, and a coin-type lithium ion secondary battery were obtained in the same manner as in Example 1, and the output characteristics and cycle characteristics were measured. The results are shown in Table 2.
- Example 7 ⁇ Production of polymer particles B-4>
- To polymerization can A 8 parts of 2-ethylhexyl acrylate, 4 parts of methyl methacrylate, 0.12 part of sodium lauryl sulfate and 79 parts of ion-exchanged water were added, 0.2 parts of ammonium persulfate as a polymerization initiator, and 10 parts of ion-exchanged water. The mixture was heated to 60 ° C.
- the emulsion prepared in this manner was sequentially added from polymerization vessel B to polymerization vessel A over about 180 minutes, and then stirred for about 120 minutes to cool the monomer when the amount of consumption reached 95%, and the reaction was terminated.
- An aqueous dispersion of B-4 was obtained.
- the obtained polymer particle B-4 had a glass transition temperature of 10 ° C. and a number average particle size of 0.1 ⁇ m. Further, the crystallinity of the polymer particle B-4 was 40% or less, and the main chain structure was a saturated structure.
- a slurry for a porous membrane, an electrode with a porous membrane, and a coin-type lithium ion secondary battery were obtained in the same manner as in Example 1 except that the polymer particle B-4 was used as the polymer particle B, and the output characteristics were obtained. And the cycle characteristics were measured. The results are shown in Table 2.
- Example 8 Except that the mass ratio of the polymer particle A-1 to the polymer particle B-1 was 75:25, the slurry for the porous film, the electrode with the porous film, and the coin type were the same as in Example 1. The lithium ion secondary battery was obtained, and the output characteristics and cycle characteristics were measured. The results are shown in Table 2.
- Example 9 The porous membrane slurry obtained in Example 1 was dried on a single-layer polypropylene separator (porosity 55%) made by a dry method having a width of 65 mm, a length of 500 mm, and a thickness of 25 ⁇ m. A porous film was formed by coating using a wire bar so that the thickness was 5 ⁇ m, and then drying at 90 ° C. for 10 minutes to obtain a separator with a porous film. A slurry for a porous film, a separator with a porous film, and a coin type, as in Example 1, except that a separator with a porous film was used as the separator and that the negative electrode was not coated with a porous film. The lithium ion secondary battery was obtained, and the output characteristics and cycle characteristics were measured. The results are shown in Table 2.
- an aromatic polyamide short fiber (copolyparaphenylene / 3,4′-oxydiphenylene / terephthalamide is used.
- a slurry for a porous film, an electrode with a porous film, and a coin-type lithium ion secondary battery were obtained, and output characteristics and cycle characteristics were measured.
- Example 14 In the preparation of the slurry for the porous membrane, in addition to the aqueous dispersion of polymer particles A and the aqueous dispersion of polymer particles B, an aromatic polyamide short fiber (copolyparaphenylene / 3,4′-oxydiphenylene / terephthalamide is used.
- slurry for porous film, electrode with porous film, and coin-type lithium ion secondary battery were obtained, and output characteristics and cycle characteristics were measured.
- Example 15 In the preparation of the slurry for the porous membrane, in addition to the aqueous dispersion of polymer particles A and the aqueous dispersion of polymer particles B, an aromatic polyamide short fiber (copolyparaphenylene / 3,4′-oxydiphenylene / terephthalamide is used.
- Example 17 The porous membrane slurry obtained in Example 10 was dried on a single-layer polypropylene separator (porosity 55%) made by a dry method having a width of 65 mm, a length of 500 mm, and a thickness of 25 ⁇ m. A porous film was formed by coating using a wire bar so that the thickness was 5 ⁇ m, and then drying at 90 ° C. for 10 minutes to obtain a separator with a porous film. A slurry for a porous film, a separator with a porous film, and a coin type, as in Example 1, except that a separator with a porous film was used as the separator and that the negative electrode was not coated with a porous film. The lithium ion secondary battery was obtained, and the output characteristics and cycle characteristics were measured. The results are shown in Table 2.
- alumina average particle diameter 300 nm, aspect ratio 1, AKP-30, manufactured by Sumitomo Chemical Co., Ltd.
- polymerization vessel B 62 parts of 2-ethylhexyl acrylate, 26 parts of methyl methacrylate, 0.3 part of sodium lauryl sulfate, and 46 parts of ion-exchanged water were added and stirred.
- the emulsion prepared in this manner was sequentially added from polymerization vessel B to polymerization vessel A over about 180 minutes, and then stirred for about 120 minutes to cool the monomer when the amount of consumption reached 95%, and the reaction was terminated.
- An aqueous dispersion of A-5 was obtained.
- the obtained polymer particle A-5 had a glass transition temperature of 10 ° C. and a number average particle diameter of 3 ⁇ m.
- a slurry for a porous membrane, an electrode with a porous membrane, and a coin-type lithium ion secondary battery were obtained in the same manner as in Example 1 except that the polymer particle A-5 was used as the polymer particle A, and the output characteristics were obtained. And the cycle characteristics were measured. The results are shown in Table 2.
- polymer particles A polymethyl methacrylate particles having a glass transition temperature of 70 ° C. and a number average particle diameter of 20 ⁇ m (manufactured by Sekisui Plastics Co., Ltd., MB-30X-20, hereinafter referred to as “polymer particles A-6”)
- polymer particles A-6 polymethyl methacrylate particles having a glass transition temperature of 70 ° C. and a number average particle diameter of 20 ⁇ m
- the emulsion prepared in this manner was sequentially added from polymerization vessel B to polymerization vessel A over about 180 minutes, and then stirred for about 120 minutes to cool the monomer when the amount of consumption reached 95%, and the reaction was terminated.
- An aqueous dispersion of B-4 was obtained.
- the obtained polymer particle B-5 had a glass transition temperature of 55 ° C. and a number average particle size of 0.1. 1 ⁇ m. Further, the crystallinity of the polymer particle B-5 was 40% or less, and the main chain structure was a saturated structure.
- the obtained polymer particle B-6 had a glass transition temperature of ⁇ 55 ° C. and a number average particle diameter of 1 ⁇ m. Further, the crystallinity of the polymer particle B-6 was 40% or less, and the main chain structure was a saturated structure.
- the emulsion prepared in this manner was sequentially added from polymerization vessel B to polymerization vessel A over about 180 minutes, and then stirred for about 120 minutes to cool the monomer when the amount of consumption reached 95%, and the reaction was terminated.
- An aqueous dispersion of B-7 was obtained.
- the obtained polymer particle B-7 had a glass transition temperature of 32 ° C. and a number average particle size of 0.1 ⁇ m. Further, the crystallinity of the polymer particle B-7 was 40% or less, and the main chain structure was a saturated structure.
- a slurry for a porous membrane, an electrode with a porous membrane, and a coin-type lithium ion secondary battery were obtained in the same manner as in Example 1 except that the polymer particle B-7 was used as the polymer particle B, and the output characteristics were obtained. And the cycle characteristics were measured. The results are shown in Table 2.
- the polymer particles A having a number average particle size of 0.4 ⁇ m or more and less than 10 ⁇ m and a glass transition point of 65 ° C. or more, and the number average particle size is By using the polymer particles B having a glass transition point of 15 ° C. or less and a temperature of 0.04 ⁇ m or more and less than 0.3 ⁇ m, a lithium secondary battery having good load characteristics and cycle characteristics can be obtained. Further, among the Examples, polystyrene particles having a glass transition temperature of 100 ° C. and a number average particle size of 3 ⁇ m as the polymer particles A, and glass transition temperatures of ⁇ 55 ° C.
- Non-conductive particles having a polymer particle A and polymer particle B ratio of 99: 1 to 85:15, a melting point of 160 ° C. or higher and an aspect ratio of 5 or higher.
- the added Examples 10, 13, and 16 have the best load characteristics and cycle characteristics.
- a polymer particle A having a glass transition temperature outside the specified range (Comparative Example 1)
- a polymer particle A having a number average particle size outside the specified range (Comparative Example 2)
- the load characteristics And at least one of the cycle characteristics is significantly inferior.
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Abstract
Description
例えば、特許文献1には、熱で電解液への膨潤度が上昇する膨潤性微粒子として架橋ポリスチレン、架橋アクリル樹脂、架橋フッ素樹脂などのポリマー粒子と、熱で溶融する熱溶融性微粒子としてポリエチレン等のポリマー粒子とを含有する多孔膜が開示されている。
また、特許文献2には、熱で電解液への膨潤度が上昇する膨潤性微粒子としてスチレン樹脂架橋体、アクリル樹脂架橋体、フッ素樹脂架橋体などのポリマー粒子と、バインダーとしてEVA、エチレン-アクリル酸共重合体、フッ素系ゴム、SBRなどの柔軟性の高いポリマーとを含有する多孔膜が開示されている。これらの多孔膜の場合は、異常発熱した際の安全性と、内部短絡に対する信頼性が向上する旨記載されている。
さらに、特許文献3には、融点が80℃から150℃の有機微粒子と、160℃以上の耐熱温度を有する耐熱微粒子を含む少なくとも2種類の微粒子が結着されて構成された多孔膜が開示されている。特許文献4には、150℃で実質的に変形しない繊維状物と、融点が80~130℃である有機微粒子を含有する多孔膜が開示されている。
従って、本発明の目的は、従来のものよりも出力特性及び長期サイクル特性が更に向上した、リチウムイオン二次電池などの二次電池に使用される多孔膜を提供することにある。
(1)数平均粒径が0.4μm以上10μm未満で、かつガラス転移点が65℃以上のポリマー粒子A、及び数平均粒径が0.04μm以上0.3μm未満で、かつガラス転移点が15℃以下のポリマー粒子Bを含んでなる二次電池用多孔膜。
(2)ポリマー粒子Bの結晶化度が40%以下で、かつ主鎖構造が飽和構造である上記(1)記載の多孔膜。
(3)融点が160℃以上である非導電性粒子をさらに含有する上記(1)又は(2)に記載の二次電池用多孔膜。
(4)前記非導電性粒子のアスペクト比が5以上である上記(3)に記載の二次電池用多孔膜。
(5)数平均粒径が0.4μm以上10μm未満で、かつガラス転移点が65℃以上のポリマー粒子A、数平均粒径が0.04μm以上0.3μm未満で、かつガラス転移点が25℃以下のポリマー粒子B及び溶媒を含んでなる二次電池用多孔膜用スラリー。
(6)数平均粒径が0.4μm以上10μm未満で、かつガラス転移点が65℃以上のポリマー粒子A、数平均粒径が0.04μm以上0.3μm未満で、かつガラス転移点が15℃以下のポリマー粒子B及び溶媒を含んでなる二次電池多孔膜用スラリーを基材に塗布する工程、スラリーが塗布された基材を乾燥する工程を含む二次電池用多孔膜の製造方法。
(7)電極合剤層用結着剤及び電極活物質を含んでなる電極合剤層が、集電体に付着してなり、かつ電極合剤層の表面に、上記(1)~(4)のいずれかに記載の多孔膜が積層されてなる二次電池用電極。
(8)有機セパレーター上に、上記(1)~(4)のいずれかに記載の多孔膜が積層されてなる二次電池用セパレーター。
(9)正極、負極、セパレーター及び電解液を含む二次電池であって、前記正極、負極及びセパレーターの少なくともいずれかに、上記(1)~(4)のいずれかに記載の多孔膜が積層されてなる、二次電池。
ポリマー粒子Bとして平均粒径0.04μm以上0.3μm未満かつガラス転移点が15℃以下のポリマー粒子を用いることにより、ポリマー粒子が電解液へ膨潤することにより、内部抵抗が低くなり、出力特性、サイクル特性が向上する。
本発明に用いるポリマー粒子Aは、平均粒径0.4μm以上10μm未満で、かつガラス転移点が65℃以上のポリマー粒子である。ポリマー粒子Aの平均粒径が0.4μm未満であると、多孔膜層として十分な膜厚を得ることができず、また、平均粒径が10μm以上であると、多孔膜層が厚くなり、内部抵抗が増加する要因となる。
なお、ポリマー粒子(ポリマー粒子A、ポリマー粒子B)の粒径は、透過型電子顕微鏡写真で無作為に選んだ粒子像100個の径を測定し、その算術平均値として算出される数平均粒子径である。
なお、ポリマー粒子(ポリマー粒子A、ポリマー粒子B)のガラス転移温度は、様々な単量体を組み合わせることによって調製可能である。ポリマー粒子(ポリマー粒子A、ポリマー粒子B)のガラス転移温度はDSCにて測定できる。
芳香族ビニル単量体やスチレン誘導体としては、スチレン、クロロスチレン、ビニルトルエン、t-ブチルスチレン、ビニル安息香酸、ビニル安息香酸メチル、ビニルナフタレン、クロロメチルスチレン、ヒドロキシメチルスチレン、α-メチルスチレン、2,4-ジメチルスチレン、ジビニルベンゼンなどが挙げられる。
また、本発明の効果を損なわない範囲において、さらに共重合可能な他の単量体を共重合させることができる。このような共重合成分としてはジエン系単量体、オレフィン系単量体、アクリレート系単量体、フッ素系単量体、ウレタン系単量体、シリコーン系単量体、ポリアミド系あるいはポリイミド系単量体、エステル系単量体などが挙げられる。
メタクリル酸エステルとしては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n-プロピル、メタクリル酸イソプロピル、メタクリル酸n-ブチル、メタクリル酸t-ブチル、及びメタクリル酸ペンチルなどが挙げられる。
本発明に用いるポリマー粒子Bは、数平均粒径0.04μm以上0.3μm未満かつガラス転移点が15℃以下のポリマー粒子である。ポリマー粒子Bの数平均粒径を上記範囲内とすることで、ポリマー粒子Aとの結着点を十分に設けることができ、高い結着性を発現することができる。ポリマー粒子Bの数平均粒径が0.04μm未満であると粒子同士が凝集しやすく、逆に0.3μm以上であると、結着点が減少し、結着性が低減する。
Xc=K・Ic/It
上記式において、Xcは被検資料の結晶化度、Icは結晶性部分からの回析X線強度、Itは全体の回析X線強度、Kは補正項を、それぞれ表す。
オキセタニル基を含有する単量体としては、3-((メタ)アクリロイルオキシメチル)オキセタン、3-((メタ)アクリロイルオキシメチル)-2-トリフロロメチルオキセタン、3-((メタ)アクリロイルオキシメチル)-2-フェニルオキセタン、2-((メタ)アクリロイルオキシメチル)オキセタン、2-((メタ)アクリロイルオキシメチル)-4-トリフロロメチルオキセタンなどが挙げられる。
オキサゾリン基を含有する単量体としては、2-ビニル-2-オキサゾリン、2-ビニル-4-メチル-2-オキサゾリン、2-ビニル-5-メチル-2-オキサゾリン、2-イソプロペニル-2-オキサゾリン、2-イソプロペニル-4-メチル-2-オキサゾリン、2-イソプロペニル-5-メチル-2-オキサゾリン、2-イソプロペニル-5-エチル-2-オキサゾリン等が挙げられる。
前記粒子状金属除去工程におけるポリマー溶液もしくはポリマー分散液から粒子状の金属成分を除去する方法は特に限定されず、例えば、濾過フィルターによる濾過により除去する方法、振動ふるいにより除去する方法、遠心分離により除去する方法、磁力により除去する方法等が挙げられる。中でも、除去対象が金属成分であるため磁力により除去する方法が好ましい。磁力により除去する方法としては、金属成分が除去できる方法であれば特に限定はされないが、生産性および除去効率を考慮すると、好ましくはポリマー粒子A及びポリマー粒子Bの製造ライン中に磁気フィルターを配置することで行われる。
無機粒子としては、酸化アルミニウム、ベーマイト、酸化鉄、酸化珪素、酸化マグネシウム、酸化チタン、BaTiO2、ZrO、アルミナ-シリカ複合酸化物等の酸化物粒子;窒化アルミニウム、窒化珪素、窒化硼素等の窒化物粒子;シリコン、ダイヤモンド等の共有結合性結晶粒子;硫酸バリウム、フッ化カルシウム、フッ化バリウム等の難溶性イオン結晶粒子;タルク、モンモリロナイトなどの粘土微粒子;ベーマイト、ゼオライト、アパタイト、カオリン、ムライト、スピネル、オリビン、セリサイト、ベントナイト等の鉱物資源由来物質あるいはそれらの人造物からなる粒子等が用いられる。これらの粒子は必要に応じて元素置換、表面処理、固溶体化等されていてもよく、また単独でも2種以上の組合せからなるものでもよい。これらの中でも電解液中での安定性と電位安定性の観点から酸化物粒子であることが好ましい。
また、これらの粒子のBET比表面積は、粒子の凝集を抑制し、後述する多孔膜用スラリーの流動性を好適化する観点から具体的には、0.9~200m2/gであることが好ましく、1.5~150m2/gであることがより好ましい。
本発明の多孔膜を製造する方法としては、1)ポリマー粒子A、ポリマー粒子B及び溶媒を含む多孔膜用スラリーを所定の基材上に塗布し、次いで乾燥する方法;2)ポリマー粒子A、ポリマー粒子B及び溶媒を含む多孔膜用スラリーに、基材を浸漬後、これを乾燥する方法;3)ポリマー粒子A、ポリマー粒子B及び溶媒を含む多孔膜用スラリーを、剥離フィルム上に塗布、乾燥し、得られた多孔膜を所定の基材上に転写する方法;が挙げられる。この中でも、1)ポリマー粒子A、ポリマー粒子B及び溶媒を含む多孔膜用スラリーを基材に塗布し、次いで乾燥する方法が、多孔膜の膜厚を制御しやすいことから最も好ましい。
(多孔膜用スラリー)
本発明の多孔膜用スラリーは、ポリマー粒子A、ポリマー粒子B、及び溶媒を含んでなる。ポリマー粒子A、ポリマー粒子Bとしては、多孔膜で説明したものを使用する。
多孔膜用スラリーに用いる溶媒としては、水および有機溶媒のいずれも使用できる。有機溶媒としては、シクロペンタン、シクロヘキサンなどの環状脂肪族炭化水素類;トルエン、キシレン、エチルベンゼンなどの芳香族炭化水素類;アセトン、エチルメチルケトン、ジイソプロピルケトン、シクロヘキサノン、メチルシクロヘキサン、エチルシクロヘキサンなどのケトン類;メチレンクロライド、クロロホルム、四塩化炭素など塩素系脂肪族炭化水素;酢酸エチル、酢酸ブチル、γ-ブチロラクトン、ε-カプロラクトンなどのエステル類;アセトニトリル、プロピオニトリルなどのアシロニトリル類;テトラヒドロフラン、エチレングリコールジエチルエーテルなどのエーテル類;メタノール、エタノール、イソプロパノール、エチレングリコール、エチレングリコールモノメチルエーテルなどのアルコール類;N-メチルピロリドン、N,N-ジメチルホルムアミドなどのアミド類があげられる。
これらの溶媒は、単独で使用しても、これらを2種以上混合して混合溶媒として使用してもよい。これらの中でも特に、ポリマーの溶解性が低いことから水が好ましい。
多孔膜用スラリーの製法は、特に限定はされず、上記ポリマー粒子A、ポリマー粒子B、及び溶媒と必要に応じ添加される他の成分を混合して得られる。
本発明においては上記成分を用いることにより混合方法や混合順序にかかわらず、ポリマー粒子A及びポリマー粒子Bが高度に分散された多孔膜用スラリーを得ることができる。混合装置は、上記成分を均一に混合できる装置であれば特に限定されず、ボールミル、サンドミル、顔料分散機、擂潰機、超音波分散機、ホモジナイザー、プラネタリーミキサーなどを使用することができるが、中でも高い分散シェアを加えることができる、ビーズミル、ロールミル、フィルミックス等の高分散装置を使用することが特に好ましい。
多孔膜用スラリーの粘度は、均一塗工性、スラリー経時安定性の観点から、好ましくは10mPa・s~10,000mPa・s、更に好ましくは50~500mPa・sである。前記粘度は、B型粘度計を用いて25℃、回転数60rpmで測定した時の値である。
本発明の多孔膜の製造方法においては、電極や有機セパレーター以外の基材上に形成してもよい。本発明の多孔膜を、電極や有機セパレーター以外の基材上に形成した場合は、多孔膜を基材から剥離し、直接電池を組み立てる時に、電極上や有機セパレーター上に積層することにより使用することができる。
乾燥方法としては例えば温風、熱風、低湿風による乾燥、真空乾燥、(遠)赤外線や電子線などの照射による乾燥法が挙げられる。乾燥温度は、使用する溶媒の種類によってかえることができる。溶媒を完全に除去するために、例えば、N-メチルピロリドン等の揮発性の低い溶媒を用いる場合には送風式の乾燥機で120℃以上の高温で乾燥させることが好ましい。逆に揮発性の高い溶媒を用いる場合には100℃以下の低温において乾燥させることもできる。多孔膜を後述する有機セパレーター上に形成する際は、有機セパレーターの収縮を起こさずに乾燥させることが必要の為、100℃以下の低温での乾燥が好ましい。
本発明の二次電池用電極は、電極合剤層用結着剤及び電極活物質を含んでなる電極合剤層が、集電体に付着してなり、かつ電極合剤層の表面に、前記多孔膜が積層されてなる。
本発明の二次電池用電極に用いられる電極活物質は、電極が利用される二次電池に応じて選択すればよい。前記二次電池としては、リチウムイオン二次電池やニッケル水素二次電池が挙げられる。
無機化合物からなる正極活物質としては、遷移金属酸化物、リチウムと遷移金属との複合酸化物、遷移金属硫化物などが挙げられる。上記の遷移金属としては、Fe、Co、Ni、Mn等が使用される。正極活物質に使用される無機化合物の具体例としては、LiCoO2、LiNiO2、LiMnO2、LiMn2O4、LiFePO4、LiFeVO4などのリチウム含有複合金属酸化物;TiS2、TiS3、非晶質MoS2等の遷移金属硫化物;Cu2V2O3、非晶質V2O-P2O5、MoO3、V2O5、V6O13などの遷移金属酸化物が挙げられる。これらの化合物は、部分的に元素置換したものであってもよい。有機化合物からなる正極活物質としては、例えば、ポリアセチレン、ポリ-p-フェニレンなどの導電性高分子を用いることもできる。電気伝導性に乏しい、鉄系酸化物は、還元焼成時に炭素源物質を存在させることで、炭素材料で覆われた電極活物質として用いてもよい。また、これら化合物は、部分的に元素置換したものであってもよい。
本発明において、電極合剤層は、電極活物質の他に、電極合剤層用結着剤を含む。電極用結着剤を含むことにより電極中の電極合剤層の結着性が向上し、電極の撒回時等の工程上においてかかる機械的な力に対する強度が上がり、また電極中の電極合剤層が脱離しにくくなることから、脱離物による短絡等の危険性が小さくなる。
ポリブチルアクリレート、ポリブチルメタクリレート、ポリヒドロキシエチルメタクリレート、ポリアクリルアミド、ポリアクリロニトリル、ブチルアクリレート・スチレン共重合体、ブチルアクリレート・アクリロニトリル共重合体、ブチルアクリレート・アクリロニトリル・グリシジルメタクリレート共重合体などの、アクリル酸またはメタクリル酸誘導体の単独重合体またはそれと共重合可能な単量体との共重合体である、アクリル系軟質重合体;
ポリイソブチレン、イソブチレン・イソプレンゴム、イソブチレン・スチレン共重合体などのイソブチレン系軟質重合体;
ポリブタジエン、ポリイソプレン、ブタジエン・スチレンランダム共重合体、イソプレン・スチレンランダム共重合体、アクリロニトリル・ブタジエン共重合体、アクリロニトリル・ブタジエン・スチレン共重合体、ブタジエン・スチレン・ブロック共重合体、スチレン・ブタジエン・スチレン・ブロック共重合体、イソプレン・スチレン・ブロック共重合体、スチレン・イソプレン・スチレン・ブロック共重合体などジエン系軟質重合体;
ジメチルポリシロキサン、ジフェニルポリシロキサン、ジヒドロキシポリシロキサンなどのケイ素含有軟質重合体;
液状ポリエチレン、ポリプロピレン、ポリ-1-ブテン、エチレン・α-オレフィン共重合体、プロピレン・α-オレフィン共重合体、エチレン・プロピレン・ジエン共重合体(EPDM)、エチレン・プロピレン・スチレン共重合体などのオレフィン系軟質重合体;
ポリビニルアルコール、ポリ酢酸ビニル、ポリステアリン酸ビニル、酢酸ビニル・スチレン共重合体などビニル系軟質重合体;
ポリエチレンオキシド、ポリプロピレンオキシド、エピクロルヒドリンゴムなどのエポキシ系軟質重合体;
フッ化ビニリデン系ゴム、四フッ化エチレン-プロピレンゴムなどのフッ素含有軟質重合体;
天然ゴム、ポリペプチド、蛋白質、ポリエステル系熱可塑性エラストマー、塩化ビニル系熱可塑性エラストマー、ポリアミド系熱可塑性エラストマーなどのその他の軟質重合体などが挙げられる。これらの軟質重合体は、架橋構造を有したものであってもよく、また、変性により官能基を導入したものであってもよい。
本発明の二次電池用セパレーターは、有機セパレーター上に、前記多孔膜が積層されてなる。
本発明に用いる有機セパレーターとしては、電子伝導性がなくイオン伝導性があり、有機溶媒の耐性が高い、孔径の微細な多孔質膜が用いられ、例えばポリオレフィン系(ポリエチレン、ポリプロピレン、ポリブテン、ポリ塩化ビニル)、及びこれらの混合物あるいは共重合体等の樹脂からなる微多孔膜、ポリエチレンテレフタレート、ポリシクロオレフィン、ポリエーテルスルフォン、ポリアミド、ポリイミド、ポリイミドアミド、ポリアラミド、ポリシクロオレフィン、ナイロン、ポリテトラフルオロエチレン等の樹脂からなる微多孔膜またはポリオレフィン系の繊維を織ったもの、またはその不織布、絶縁性物質粒子の集合体等が挙げられる。これらの中でも、前述の多孔膜用スラリーの塗工性が優れ、セパレーター全体の膜厚を薄くし電池内の活物質比率を上げて体積あたりの容量を上げることができるため、ポリオレフィン系の樹脂からなる微多孔膜が好ましい。
有機セパレーターの厚さは、通常0.5~40μm、好ましくは1~30μm、更に好ましくは1~10μmである。この範囲であると電池内でのセパレーターによる抵抗が小さくなり、また有機セパレーターへの塗工時の作業性が良い。
本発明の二次電池は、正極、負極、セパレーター及び電解液を含み、前記正極、負極及びセパレーターの少なくともいずれかに、前記多孔膜が積層されてなる。
リチウムイオン二次電池用の電解液としては、有機溶媒に支持電解質を溶解した有機電解液が用いられる。支持電解質としては、リチウム塩が用いられる。リチウム塩としては、特に制限はないが、LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLiなどが挙げられる。中でも、溶媒に溶けやすく高い解離度を示すLiPF6、LiClO4、CF3SO3Liが好ましい。これらは、二種以上を併用してもよい。解離度の高い支持電解質を用いるほどリチウムイオン伝導度が高くなるので、支持電解質の種類によりリチウムイオン伝導度を調節することができる。
また前記電解液には添加剤を含有させて用いることも可能である。添加剤としては前述の電極合剤層スラリー中に使用されるビニレンカーボネート(VC)などのカーボネート系の化合物が挙げられる。
上記以外の電解液としては、ポリエチレンオキシド、ポリアクリロニトリルなどのポリマー電解質や前記ポリマー電解質に電解液を含浸したゲル状ポリマー電解質や、LiI、Li3Nなどの無機固体電解質を挙げることができる。
本発明の二次電池において、多孔膜が積層されてなる正極や負極としては、前記二次電池用電極を正極や負極として用いればよく、多孔膜が積層されてなるセパレーターとしては、前記二次電池用セパレーターをセパレーターとして用いればよい。
以下に、実施例を挙げて本発明を説明するが、本発明はこれに限定されるものではない。尚、本実施例における部および%は、特記しない限り質量基準である。
実施例および比較例において、各種物性は以下のように評価する。
得られたコイン型のリチウムイオン二次電池を用いて、25℃で0.1Cの定電流法によって4.3Vまで充電しその後0.1Cにて3.0Vまで放電し、0.1C放電容量を求める。その後、0.1Cにて4.3Vまで充電しその後5C、10C、20Cにて3.0Vまで放電し、5C、10C、20C放電容量を求める。これらの測定をフルセルコイン型電池10セルについて行い、各測定値の平均値を、0.1C放電容量a、5C、10C、20C放電容量bとする。5C、10C、20C放電容量bと0.1C放電容量aの電気容量の比(b/a(%))で表される容量保持率を求め、これを出力特性の評価基準とし、以下の基準により判定する。この値が高いほど出力特性に優れている。
SA:60%以上
A:50%以上60%未満
B:30%以上50%未満
C:10%以上30%未満
D:1%以上10%未満
E:1%未満
得られたコイン型のリチウムイオン二次電池を用いて、25℃及び60℃それぞれにおいて、0.1Cで3Vから4.3Vまで充電し、次いで0.1Cで4.3Vから3Vまで放電する充放電を、100サイクル繰り返し、5サイクル目の0.1C放電容量に対する100サイクル目の0.1C放電容量の割合を百分率で算出した値を容量維持率とし、下記の基準で判断する。この値が大きいほど放電容量減が少なく、長期サイクル特性に優れている。
SA:80%以上
A:70%以上80%未満
B:60%以上70%未満
C:50%以上60%未満
D:40%以上50%未満
E:30%以上40%未満
F:30%未満
ポリマー粒子A-1として、数平均粒径3μm、ガラス転移温度が100℃のポリスチレン粒子(Spherotech社製PP-30-10)を用いた。
重合缶Aに、n-ブチルアクリレート12部、ラウリル硫酸ナトリウム0.12部、イオン交換水79部を加え、重合開始剤として過硫酸アンモニウム0.2部、イオン交換水10部を加え60℃に加温し90分攪拌した後に、別の重合缶Bにn-ブチルアクリレート88部、ラウリル硫酸ナトリウム0.9部、イオン交換水46部を加えて攪拌して作製したエマルジョンを約180分かけて重合缶Bから重合缶Aに逐次添加した後、約120分攪拌してモノマー消費量が95%になったところで冷却して反応を終了し、ポリマー粒子B-1の水分散液を得た。得られたポリマー粒子B-1のガラス転移温度は-55℃、数平均粒子径は0.1μmであった。また、ポリマー粒子B-1の結晶化度は40%以下で、主鎖構造が飽和構造であった。
ポリマー粒子Aの水分散液とポリマー粒子Bの水分散液を、ポリマー粒子A-1とポリマー粒子B-1との質量比率(固形分基準)が、表1に記載の比率、すなわち97:3になるように混合し、固形分濃度13%の多孔膜用スラリーを得た。
負極活物質として粒子径20μm、比表面積4.2m2/gのグラファイト98部と、電極合剤層用結着剤としてPVDF(ポリフッ化ビニリデン)を固形分相当で5部とを混合し、更にN-メチルピロリドンを加えてプラネタリーミキサーで混合してスラリー状の負極用電極組成物(負極合剤層形成用スラリー)を調製した。この負極用電極組成物を厚さ10μmの銅箔の片面に塗布し、110℃で3時間乾燥した後、ロールプレスして厚さ60μmの負極合剤層を有する負極を得た。
正極活物質としてスピネル構造を有するマンガン酸リチウム92部と、アセチレンブラック5部、電極合剤層用結着剤としてPVDF(ポリフッ化ビニリデン)を固形分相当で3部とを加え、さらにNMPで固形分濃度87%に調整した後にプラネタリーミキサーで60分混合した。さらにNMPで固形分濃度84%に調整した後に10分間混合してスラリー状の正極用電極組成物(正極合剤層形成用スラリー)を調製した。この正極用電極組成物を厚さ18μmのアルミニウム箔に塗布し、120℃で3時間乾燥した後、ロールプレスして厚さ50μmの正極合剤層を有する正極を得た。
得られた負極の負極合剤層上に多孔膜用スラリーを乾燥後の多孔膜層の厚さが5μmになるようにワイヤーバーを用いて塗工し、次いで90℃で10分間乾燥することにより、多孔膜を形成し、多孔膜付負極を得た。
次いで、得られた正極を直径13mm、多孔膜付負極1を直径14mm、厚さ25μmの乾式法により製造された単層のポリプロピレン製セパレーター(気孔率55%)を直径18mmの円形に切り抜いた。正極電極の正極合剤層面側に、セパレーターを介在させ、互いに電極合剤層が対向し、外装容器底面に正極のアルミニウム箔が接触するように多孔膜付負極を配置し、更に負極の銅箔上にエキスパンドメタルを入れ、ポリプロピレン製パッキンを設置したステンレス鋼製のコイン型外装容器(直径20mm、高さ1.8mm、ステンレス鋼厚さ0.25mm)中に収納した。この容器中に電解液(EC/DEC=1/2、1M LiPF6)を空気が残らないように注入し、ポリプロピレン製パッキンを介して外装容器に厚さ0.2mmのステンレス鋼のキャップをかぶせて固定し、電池缶を封止して、直径20mm、厚さ約3.2mmのフルセル型コインセルを製造した(コインセルCR2032)。得られた電池について出力特性、サイクル特性を測定した。結果を表1に示す。
ポリマー粒子Aとして、ガラス転移温度が100℃で、数平均粒径が7μmのポリスチレン粒子(Spherotech社製、PP-60-10、以下「ポリマー粒子A-2」と記すことがある。)を用いたこと以外は、実施例1と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。結果を表1に示す。
ポリマー粒子Aとして、ガラス転移温度が100℃、数平均粒径が0.5μmのポリスチレン粒子(Spherotech社製、PP-05-10、以下「ポリマー粒子A-3」と記すことがある。)を用いたこと以外は、実施例1と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。結果を表2に示す。
<ポリマー粒子B-2の製造>
重合缶Aに、n-ブチルアクリレート12部、ラウリル硫酸ナトリウム0.12部、イオン交換水79部を加え、重合開始剤として過硫酸アンモニウム0.2部、イオン交換水10部を加え60℃に加温し90分攪拌した後に、別の重合缶Bにn-ブチルアクリレート88部、ラウリル硫酸ナトリウム0.3部、イオン交換水46部を加えて攪拌して作製したエマルジョンを約180分かけて重合缶Bから重合缶Aに逐次添加した後、約120分攪拌してモノマー消費量が95%になったところで冷却して反応を終了し、ポリマー粒子B-2の水分散液を得た。得られたポリマー粒子B-2のガラス転移温度は-55℃、数平均粒子径は0.3μmであった。また、ポリマー粒子B-2の結晶化度は40%以下で、主鎖構造が飽和構造であった。
<ポリマー粒子B-3の製造>
重合缶Aに、n-ブチルアクリレート12部、ラウリル硫酸ナトリウム0.12部、イオン交換水79部を加え、重合開始剤として過硫酸アンモニウム0.2部、イオン交換水10部を加え60℃に加温し90分攪拌した後に、別の重合缶Bにn-ブチルアクリレート88部、ラウリル硫酸ナトリウム2.7部、イオン交換水46部を加えて攪拌して作製したエマルジョンを約180分かけて重合缶Bから重合缶Aに逐次添加した後、約120分攪拌してモノマー消費量が95%になったところで冷却して反応を終了し、ポリマー粒子B-3の水分散液を得た。得られたポリマー粒子B-3のガラス転移温度は-55℃、数平均粒子径は0.05μmであった。また、ポリマー粒子B-3の結晶化度は40%以下で、主鎖構造が飽和構造であった。
ポリマー粒子Aとして、ガラス転移温度が70℃で、数平均粒径が3μmのポリメタクリル酸メチル粒子(綜研化学社製、MX-300、以下「ポリマー粒子A-4」と記すことがある。)を用いたこと以外は、実施例1と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。結果を表2に示す。
<ポリマー粒子B-4の製造>
重合缶Aに、2-エチルヘキシルアクリレート8部、メタクリル酸メチル4部、ラウリル硫酸ナトリウム0.12部、イオン交換水79部を加え、重合開始剤として過硫酸アンモニウム0.2部、イオン交換水10部を加え60℃に加温し90分攪拌した後に、別の重合缶Bに2-エチルヘキシルアクリレート62部、メタクリル酸メチル26部、ラウリル硫酸ナトリウム0.9部、イオン交換水46部を加えて攪拌して作製したエマルジョンを約180分かけて重合缶Bから重合缶Aに逐次添加した後、約120分攪拌してモノマー消費量が95%になったところで冷却して反応を終了し、ポリマー粒子B-4の水分散液を得た。得られたポリマー粒子B-4のガラス転移温度は10℃、数平均粒子径は0.1μmであった。また、ポリマー粒子B-4の結晶化度は40%以下で、主鎖構造が飽和構造であった。
ポリマー粒子A-1とポリマー粒子B-1との質量比率が、75:25になるようにしたこと以外は、実施例1と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。結果を表2に示す。
実施例1で得られた多孔膜スラリーを、幅65mm、長さ500mm、厚さ25μmの乾式法により製造された単層のポリプロピレン製セパレーター(気孔率55%)上に乾燥後の多孔膜層の厚さが5μmになるようにワイヤーバーを用いて塗工し、次いで90℃で10分間乾燥することにより、多孔膜を形成し、多孔膜付セパレーターを得た。
セパレーターとして多孔膜付セパレーターを使用し、負極としては多孔膜を塗工していないものを使用したこと以外は、実施例1と同様にして、多孔膜用スラリー、多孔膜付セパレーター、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。結果を表2に示す。
多孔膜用スラリーの調製において、ポリマー粒子Aの水分散液、ポリマー粒子Bの水分散液に加えて板状ベーマイト(平均粒子径1μm、アスペクト比10)を、ポリマー粒子(ポリマー粒子A-1及びポリマー粒子B-1)と、板状ベーマイトとの質量比率が、ポリマー粒子:板状ベーマイト=30:70となるように加え、固形分濃度25%の多孔膜用スラリーを得たこと以外は、実施例1と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。
多孔膜用スラリーの調製において、ポリマー粒子Aの水分散液、ポリマー粒子Bの水分散液に加えて板状ベーマイト(平均粒子径1μm、アスペクト比10)を、ポリマー粒子(ポリマー粒子A-2及びポリマー粒子B-1)と、板状ベーマイトとの質量比率が、ポリマー粒子:板状ベーマイト=30:70となるように加え、固形分濃度25%の多孔膜用スラリーを得たこと以外は、実施例2と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。
多孔膜用スラリーの調製において、ポリマー粒子Aの水分散液、ポリマー粒子Bの水分散液に加えて板状ベーマイト(平均粒子径1μm、アスペクト比10)を、ポリマー粒子(ポリマー粒子A-1及びポリマー粒子B-1)と、板状ベーマイトとの質量比率が、ポリマー粒子:板状ベーマイト=30:70となるように加え、固形分濃度25%の多孔膜用スラリーを得たこと以外は、実施例8と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。
多孔膜用スラリーの調製において、ポリマー粒子Aの水分散液、ポリマー粒子Bの水分散液に加えて、芳香族ポリアミド短繊維(コポリパラフェニレン・3,4’-オキシジフェニレン・テレフタルアミドからなる単繊維繊度:0.55dtex(0.5de)、カット長:1mmの短繊維、アスペクト比200、融点187℃、帝人社製、「テクノーラ」)を、ポリマー粒子(ポリマー粒子A-1及びポリマー粒子B-1)と、芳香族ポリアミド繊維との質量比率が、ポリマー粒子:芳香族ポリアミド繊維=50:50となるように加え、固形分濃度20%の多孔膜用スラリーを得たこと以外は、実施例1と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。
多孔膜用スラリーの調製において、ポリマー粒子Aの水分散液、ポリマー粒子Bの水分散液に加えて、芳香族ポリアミド短繊維(コポリパラフェニレン・3,4’-オキシジフェニレン・テレフタルアミドからなる単繊維繊度:0.55dtex(0.5de)、カット長:1mmの短繊維、アスペクト比200、融点187℃、帝人社製、「テクノーラ」)を、ポリマー粒子(ポリマー粒子A-2及びポリマー粒子B-1)と、芳香族ポリアミド繊維との質量比率が、ポリマー粒子:芳香族ポリアミド繊維=50:50となるよう加え、固形分濃度20%の多孔膜用スラリーを得たこと以外は、実施例2と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。
多孔膜用スラリーの調製において、ポリマー粒子Aの水分散液、ポリマー粒子Bの水分散液に加えて、芳香族ポリアミド短繊維(コポリパラフェニレン・3,4’-オキシジフェニレン・テレフタルアミドからなる単繊維繊度:0.55dtex(0.5de)、カット長:1mmの短繊維、アスペクト比200、帝人社製、「テクノーラ」)を、ポリマー粒子(ポリマー粒子A-1及びポリマー粒子B-1)と、芳香族ポリアミド繊維との質量比率が、ポリマー粒子:芳香族ポリアミド繊維=50:50となるように加え、固形分濃度20%の多孔膜用スラリーを得たこと以外は、実施例8と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。
多孔膜用スラリーの調製において、ポリマー粒子Aの水分散液、ポリマー粒子Bの水分散液に加えてポリフェニレンスルファイド短繊維(融点285℃、単繊維繊度:0.55dtex(0.5de)、カット長:1mmの短繊維、アスペクト比200)を、ポリマー粒子(ポリマー粒子A-1及びポリマー粒子B-1)と、ポリフェニレンスルファイド短繊維との質量比率が、ポリマー粒子:ポリフェニレンスルファイド短繊維=30:70となるよう加え、固形分濃度20%の多孔膜用スラリーを得たこと以外は、実施例1と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。
実施例10で得られた多孔膜スラリーを、幅65mm、長さ500mm、厚さ25μmの乾式法により製造された単層のポリプロピレン製セパレーター(気孔率55%)上に乾燥後の多孔膜層の厚さが5μmになるようにワイヤーバーを用いて塗工し、次いで90℃で10分間乾燥することにより、多孔膜を形成し、多孔膜付セパレーターを得た。
セパレーターとして多孔膜付セパレーターを使用し、負極としては多孔膜を塗工していないものを使用したこと以外は、実施例1と同様にして、多孔膜用スラリー、多孔膜付セパレーター、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。結果を表2に示す。
多孔膜用スラリーの調製において、ポリマー粒子Aの水分散液、ポリマー粒子Bの水分散液に加えてアルミナ(平均粒子径300nm、アスペクト比1、AKP-30、住友化学社製、)を、ポリマー粒子(ポリマー粒子A-1及びポリマー粒子B-1)と、アルミナとの質量比率が、ポリマー粒子:アルミナ=30:70となるように加え、固形分濃度25%の多孔膜用スラリーを得たこと以外は、実施例1と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。
<ポリマー粒子A-5の製造>
重合缶Aに、2-エチルヘキシルアクリレート8部、メタクリル酸メチル4部、ラウリル硫酸ナトリウム0.04部、イオン交換水79部を加え、重合開始剤として過硫酸アンモニウム0.2部、イオン交換水10部を加え60℃に加温し90分攪拌した後に、別の重合缶Bに2-エチルヘキシルアクリレート62部、メタクリル酸メチル26部、ラウリル硫酸ナトリウム0.3部、イオン交換水46部を加えて攪拌して作製したエマルジョンを約180分かけて重合缶Bから重合缶Aに逐次添加した後、約120分攪拌してモノマー消費量が95%になったところで冷却して反応を終了し、ポリマー粒子A-5の水分散液を得た。得られたポリマー粒子A-5のガラス転移温度は10℃、数平均粒子径は3μmであった。
ポリマー粒子Aとして、ガラス転移温度が70℃で、数平均粒径が20μmのポリメタクリル酸メチル粒子(積水化成品工業社製、MB-30X-20、以下「ポリマー粒子A-6」と記すことがある。)を用いたこと以外は、実施例1と同様にして、多孔膜用スラリー、多孔膜付電極、及びコイン型のリチウムイオン二次電池を得、出力特性及びサイクル特性を測定した。結果を表2に示す。
<ポリマー粒子B-5の製造>
重合缶Aに、2-エチルヘキシルアクリレート5部、メタクリル酸メチル7部、ラウリル硫酸ナトリウム0.12部、イオン交換水79部を加え、重合開始剤として過硫酸アンモニウム0.2部、イオン交換水10部を加え60℃に加温し90分攪拌した後に、別の重合缶Bに2-エチルヘキシルアクリレート35部、メタクリル酸メチル53部、ラウリル硫酸ナトリウム0.9部、イオン交換水46部を加えて攪拌して作製したエマルジョンを約180分かけて重合缶Bから重合缶Aに逐次添加した後、約120分攪拌してモノマー消費量が95%になったところで冷却して反応を終了し、ポリマー粒子B-4の水分散液を得た。得られたポリマー粒子B-5のガラス転移温度は55℃、数平均粒子径は0. 1μmであった。また、ポリマー粒子B-5の結晶化度は40%以下で、主鎖構造は飽和構造であった。
<ポリマー粒子B-6の製造>
重合缶Aに、n-ブチルアクリレート12部、ラウリル硫酸ナトリウム0.12部、イオン交換水79部を加え、重合開始剤として過硫酸アンモニウム0.2部、イオン交換水10部を加え60℃に加温し90分攪拌した後に、別の重合缶Bにn-ブチルアクリレート88部、ラウリル硫酸ナトリウム0.2部、イオン交換水46部を加えて攪拌して作製したエマルジョンを約180分かけて重合缶Bから重合缶Aに逐次添加した後、約120分攪拌してモノマー消費量が95%になったところで冷却して反応を終了し、ポリマー粒子B-6の水分散液を得た。得られたポリマー粒子B-6のガラス転移温度は-55℃、数平均粒子径は1μmであった。また、ポリマー粒子B-6の結晶化度は40%以下で、主鎖構造は飽和構造であった。
<ポリマー粒子B-7の製造>
重合缶Aに、2-エチルヘキシルアクリレート5部、メタクリル酸メチル7部、ラウリル硫酸ナトリウム0.12部、イオン交換水79部を加え、重合開始剤として過硫酸アンモニウム0.2部、イオン交換水10部を加え60℃に加温し90分攪拌した後に、別の重合缶Bに2-エチルヘキシルアクリレート50部、メタクリル酸メチル38部、ラウリル硫酸ナトリウム0.9部、イオン交換水46部を加えて攪拌して作製したエマルジョンを約180分かけて重合缶Bから重合缶Aに逐次添加した後、約120分攪拌してモノマー消費量が95%になったところで冷却して反応を終了し、ポリマー粒子B-7の水分散液を得た。得られたポリマー粒子B-7のガラス転移温度は32℃、数平均粒子径は0.1μmであった。また、ポリマー粒子B-7の結晶化度は40%以下で、主鎖構造は飽和構造であった。
Claims (9)
- 数平均粒径が0.4μm以上10μm未満で、かつガラス転移点が65℃以上のポリマー粒子A、及び数平均粒径が0.04μm以上0.3μm未満で、かつガラス転移点が15℃以下のポリマー粒子Bを含んでなる二次電池用多孔膜。
- ポリマー粒子Bの結晶化度が40%以下で、かつ主鎖構造が飽和構造である請求項1記載の二次電池用多孔膜。
- 融点が160℃以上である非導電性粒子をさらに含有する請求項1又は請求項2に記載の二次電池用多孔膜。
- 前記非導電性粒子のアスペクト比が5以上である請求項3に記載の二次電池用多孔膜。
- 数平均粒径が0.4μm以上10μm未満で、かつガラス転移点が65℃以上のポリマー粒子A、数平均粒径が0.04μm以上0.3μm未満で、かつガラス転移点が15℃以下のポリマー粒子B及び溶媒を含んでなる二次電池多孔膜用スラリー。
- 数平均粒径が0.4μm以上10μm未満で、かつガラス転移点が65℃以上のポリマー粒子A、数平均粒径が0.04μm以上0.3μm未満で、かつガラス転移点が15℃以下のポリマー粒子B及び溶媒を含んでなる二次電池多孔膜用スラリーを基材に塗布する工程、スラリーが塗布された基材を乾燥する工程を含む二次電池用多孔膜の製造方法。
- 電極合剤層用結着剤及び電極活物質を含んでなる電極合剤層が、集電体に付着してなり、かつ電極合剤層の表面に、請求項1~4のいずれかに記載の多孔膜が積層されてなる二次電池用電極。
- 有機セパレーター上に、請求項1~4のいずれかに記載の多孔膜が積層されてなる二次電池用セパレーター。
- 正極、負極、セパレーター及び電解液を含む二次電池であって、前記正極、負極及びセパレーターの少なくともいずれかに、請求項1~4のいずれかに記載の多孔膜が積層されてなる、二次電池。
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Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6114160A (ja) * | 1984-06-29 | 1986-01-22 | 大和石油株式会社 | セメント混合物硬化体の耐水、耐凍結並びにクリ−プ発生抑制剤組成物及び相乗的処理方法 |
JPS6123637A (ja) * | 1984-07-11 | 1986-02-01 | Japan Synthetic Rubber Co Ltd | 重合体粒子の製造方法 |
JPH03291848A (ja) * | 1990-04-09 | 1991-12-24 | Asahi Chem Ind Co Ltd | 電池 |
WO1997001870A1 (fr) * | 1995-06-28 | 1997-01-16 | Fuji Photo Film Co., Ltd. | Batterie bivalente non aqueuse |
JPH0987571A (ja) * | 1995-09-25 | 1997-03-31 | Nippon Zeon Co Ltd | 有機溶媒系バインダー組成物、電極、および電池 |
JPH11131392A (ja) * | 1997-11-05 | 1999-05-18 | Oji Paper Co Ltd | 印刷用艶消し塗被紙 |
JP2004241135A (ja) * | 2003-02-03 | 2004-08-26 | Matsushita Electric Ind Co Ltd | 二次電池およびその製造法 |
JP2005336353A (ja) * | 2004-05-27 | 2005-12-08 | Bridgestone Corp | パンクシーリング剤 |
JP2006139978A (ja) | 2004-11-11 | 2006-06-01 | Hitachi Maxell Ltd | 非水電池およびその製造方法 |
JP2006164761A (ja) | 2004-12-08 | 2006-06-22 | Hitachi Maxell Ltd | セパレータおよびその製造方法、並びに非水電解質電池 |
WO2007066768A1 (ja) * | 2005-12-08 | 2007-06-14 | Hitachi Maxell, Ltd. | 電気化学素子用セパレータとその製造方法、並びに電気化学素子とその製造方法 |
US20070264577A1 (en) | 2004-12-08 | 2007-11-15 | Hideaki Katayama | Separator for Electrochemical Device, and Electrochemical Device |
JP2008004441A (ja) | 2006-06-23 | 2008-01-10 | Hitachi Maxell Ltd | リチウム二次電池、リチウム二次電池用セパレータ、リチウム二次電池用電極、リチウム二次電池用非水電解液およびリチウム二次電池用外装体 |
JP2008287888A (ja) * | 2007-05-15 | 2008-11-27 | Asahi Kasei Chemicals Corp | 非水電解液二次電池用コーティング組成物 |
JP2008546135A (ja) * | 2005-05-17 | 2008-12-18 | エルジー・ケム・リミテッド | 多重積層電気化学セルを含む電気化学素子用のバインダー |
JP2010027218A (ja) * | 2008-07-15 | 2010-02-04 | Hitachi Maxell Ltd | 非水電解質電池用セパレータおよび非水電解質電池 |
WO2010134501A1 (ja) * | 2009-05-18 | 2010-11-25 | 日本ゼオン株式会社 | 多孔膜及び二次電池 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1269487A (en) * | 1984-07-11 | 1990-05-22 | Nobuyuki Ito | Polymer particles and process for producing the same |
KR20000049093A (ko) * | 1996-10-11 | 2000-07-25 | 자르밀라 제트. 흐르벡 | 배터리용 중합체 전해질, 인터칼레이션 화합물 및 전극 |
US8507124B2 (en) * | 2007-11-14 | 2013-08-13 | Toray Battery Separator Film Co., Ltd. | Multi-layer, microporous membrane, battery separator and battery |
WO2010024328A1 (ja) * | 2008-08-29 | 2010-03-04 | 日本ゼオン株式会社 | 多孔膜、二次電池電極及びリチウムイオン二次電池 |
JP5444781B2 (ja) * | 2009-03-25 | 2014-03-19 | Tdk株式会社 | リチウムイオン二次電池用電極及びリチウムイオン二次電池 |
-
2010
- 2010-09-30 EP EP10820677.2A patent/EP2485295B1/en active Active
- 2010-09-30 US US13/498,993 patent/US20120189897A1/en not_active Abandoned
- 2010-09-30 WO PCT/JP2010/067137 patent/WO2011040562A1/ja active Application Filing
- 2010-09-30 HU HUE10820677A patent/HUE043623T2/hu unknown
- 2010-09-30 KR KR1020127008102A patent/KR20120091028A/ko not_active Application Discontinuation
- 2010-09-30 JP JP2011534328A patent/JP5742717B2/ja active Active
- 2010-09-30 PL PL10820677T patent/PL2485295T3/pl unknown
- 2010-09-30 CN CN201080054112.5A patent/CN102630353B/zh active Active
Patent Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6114160A (ja) * | 1984-06-29 | 1986-01-22 | 大和石油株式会社 | セメント混合物硬化体の耐水、耐凍結並びにクリ−プ発生抑制剤組成物及び相乗的処理方法 |
JPS6123637A (ja) * | 1984-07-11 | 1986-02-01 | Japan Synthetic Rubber Co Ltd | 重合体粒子の製造方法 |
JPH03291848A (ja) * | 1990-04-09 | 1991-12-24 | Asahi Chem Ind Co Ltd | 電池 |
WO1997001870A1 (fr) * | 1995-06-28 | 1997-01-16 | Fuji Photo Film Co., Ltd. | Batterie bivalente non aqueuse |
JPH0987571A (ja) * | 1995-09-25 | 1997-03-31 | Nippon Zeon Co Ltd | 有機溶媒系バインダー組成物、電極、および電池 |
JPH11131392A (ja) * | 1997-11-05 | 1999-05-18 | Oji Paper Co Ltd | 印刷用艶消し塗被紙 |
JP2004241135A (ja) * | 2003-02-03 | 2004-08-26 | Matsushita Electric Ind Co Ltd | 二次電池およびその製造法 |
JP2005336353A (ja) * | 2004-05-27 | 2005-12-08 | Bridgestone Corp | パンクシーリング剤 |
JP2006139978A (ja) | 2004-11-11 | 2006-06-01 | Hitachi Maxell Ltd | 非水電池およびその製造方法 |
JP2006164761A (ja) | 2004-12-08 | 2006-06-22 | Hitachi Maxell Ltd | セパレータおよびその製造方法、並びに非水電解質電池 |
US20070264577A1 (en) | 2004-12-08 | 2007-11-15 | Hideaki Katayama | Separator for Electrochemical Device, and Electrochemical Device |
JP2008546135A (ja) * | 2005-05-17 | 2008-12-18 | エルジー・ケム・リミテッド | 多重積層電気化学セルを含む電気化学素子用のバインダー |
WO2007066768A1 (ja) * | 2005-12-08 | 2007-06-14 | Hitachi Maxell, Ltd. | 電気化学素子用セパレータとその製造方法、並びに電気化学素子とその製造方法 |
JP2008305783A (ja) | 2005-12-08 | 2008-12-18 | Hitachi Maxell Ltd | 電気化学素子用セパレータとその製造方法、並びに電気化学素子とその製造方法 |
US20090067119A1 (en) | 2005-12-08 | 2009-03-12 | Hideaki Katayama | Separator for electrochemical device and method for producing the same, and electrochemical device and method for producing the same |
JP2008004441A (ja) | 2006-06-23 | 2008-01-10 | Hitachi Maxell Ltd | リチウム二次電池、リチウム二次電池用セパレータ、リチウム二次電池用電極、リチウム二次電池用非水電解液およびリチウム二次電池用外装体 |
JP2008287888A (ja) * | 2007-05-15 | 2008-11-27 | Asahi Kasei Chemicals Corp | 非水電解液二次電池用コーティング組成物 |
JP2010027218A (ja) * | 2008-07-15 | 2010-02-04 | Hitachi Maxell Ltd | 非水電解質電池用セパレータおよび非水電解質電池 |
WO2010134501A1 (ja) * | 2009-05-18 | 2010-11-25 | 日本ゼオン株式会社 | 多孔膜及び二次電池 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2485295A4 |
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EP2728646A4 (en) * | 2011-07-01 | 2015-03-11 | Zeon Corp | POROUS FILM FOR SECONDARY BATTERY, AND MANUFACTURING METHOD AND APPLICATION THEREOF |
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JP7094968B2 (ja) | 2017-12-11 | 2022-07-04 | エルジー エナジー ソリューション リミテッド | セパレータ及びそれを含む電気化学素子 |
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JP2021520607A (ja) * | 2018-04-03 | 2021-08-19 | シャンハイ、エナジー、ニュー、マテリアルズ、テクノロジー、カンパニー、リミテッドShanghai Energy New Materials Technology Co., Ltd. | セパレータを製造するためのコーティングスラリー、電気化学デバイスのためのセパレータ及びその製造方法 |
JP2018170281A (ja) * | 2018-05-31 | 2018-11-01 | 旭化成株式会社 | 蓄電デバイス用セパレータ、蓄電デバイス及びリチウムイオン二次電池 |
JP7082202B2 (ja) | 2018-07-10 | 2022-06-07 | 帝人株式会社 | 非水系二次電池用バインダおよびその分散液 |
WO2020012990A1 (ja) * | 2018-07-10 | 2020-01-16 | 帝人株式会社 | 非水系二次電池用バインダおよびその分散液 |
JPWO2020012990A1 (ja) * | 2018-07-10 | 2021-06-03 | 帝人株式会社 | 非水系二次電池用バインダおよびその分散液 |
US12095091B2 (en) | 2018-07-10 | 2024-09-17 | Teijin Limited | Binder for non-aqueous secondary battery and dispersion thereof |
JP2023508241A (ja) * | 2020-11-30 | 2023-03-01 | 寧徳時代新能源科技股▲分▼有限公司 | セパレータ、その製造方法およびそれに関連する二次電池、電池モジュール、電池パックならびに装置 |
JP2023508242A (ja) * | 2020-11-30 | 2023-03-01 | 寧徳時代新能源科技股▲分▼有限公司 | セパレータ、それを含む二次電池および装置 |
JP7446459B2 (ja) | 2020-11-30 | 2024-03-08 | 寧徳時代新能源科技股▲分▼有限公司 | セパレータ、その製造方法およびそれに関連する二次電池、電池モジュール、電池パックならびに装置 |
JP7451745B2 (ja) | 2020-11-30 | 2024-03-18 | 寧徳時代新能源科技股▲分▼有限公司 | セパレータ、それを含む二次電池および装置 |
WO2023008319A1 (ja) * | 2021-07-30 | 2023-02-02 | 日本ゼオン株式会社 | 電気化学素子機能層用組成物及びその製造方法、電気化学素子用機能層及び電気化学素子 |
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Publication number | Publication date |
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JPWO2011040562A1 (ja) | 2013-02-28 |
CN102630353A (zh) | 2012-08-08 |
KR20120091028A (ko) | 2012-08-17 |
US20120189897A1 (en) | 2012-07-26 |
EP2485295A4 (en) | 2014-05-21 |
PL2485295T3 (pl) | 2019-08-30 |
EP2485295A1 (en) | 2012-08-08 |
EP2485295B1 (en) | 2019-03-20 |
JP5742717B2 (ja) | 2015-07-01 |
HUE043623T2 (hu) | 2019-08-28 |
CN102630353B (zh) | 2014-12-10 |
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