CN103262297B - Secondary-battery porous-membrane slurry, secondary-battery porous membrane, secondary-battery electrode, secondary-battery separator, secondary battery, and method for manufacturing secondary-battery porous membrane - Google Patents

Secondary-battery porous-membrane slurry, secondary-battery porous membrane, secondary-battery electrode, secondary-battery separator, secondary battery, and method for manufacturing secondary-battery porous membrane Download PDF

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CN103262297B
CN103262297B CN201180057676.9A CN201180057676A CN103262297B CN 103262297 B CN103262297 B CN 103262297B CN 201180057676 A CN201180057676 A CN 201180057676A CN 103262297 B CN103262297 B CN 103262297B
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polymer particles
perforated membrane
acrylic polymer
secondary cell
quality
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CN103262297A (en
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金田拓也
石井琢也
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Zeon Corp
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Nippon Zeon Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

To provide a high-strength, highly uniform secondary-battery porous membrane that is capable of improving the cycle characteristics of a resulting secondary battery and is manufactured using a secondary-battery porous-membrane slurry that exhibits excellent coating performance and contains highly-dispersed nonconductive particles. Also, to provide a secondary-battery electrode and secondary-battery separator having good shutdown functionality. This secondary-battery porous-membrane slurry is characterized by containing organic-polymer-containing nonconductive particles, a binder, and a solvent, and is further characterized in that said binder contains particles (A) of an acrylic polymer that has a sulfonic acid group and particles (B) of an acrylic polymer that has an epoxy group.

Description

The manufacture method of secondary cell perforated membrane slurry, secondary cell perforated membrane, electrode for secondary battery, secondary battery separator, secondary cell and secondary cell perforated membrane
Technical field
The present invention relates to a kind of secondary cell perforated membrane slurry, further specifically, a kind of surface of electrode or dividing plate for the manufacture of being formed at lithium rechargeable battery, reliability is related to high and the secondary cell perforated membrane slurry of the secondary cell perforated membrane of the improvement of the cycle characteristics of battery can be contributed to.In addition, the present invention relates to a kind of electrode for secondary battery, secondary battery separator and the secondary cell that possess this secondary cell perforated membrane.
Background technology
In practical battery, the energy density that lithium rechargeable battery display is the highest, is particularly used for miniaturized electronics and uses.In addition, except small utility, also expect to use in automobile.Wherein, the long lifetime of lithium rechargeable battery and the further raising of fail safe is expected.
Lithium rechargeable battery generally for the short circuit prevented between positive pole and negative pole, uses the organic dividing plate of the polyolefin such as polyethylene and polypropylene.Because the organic dividing plate of polyolefin has the physical property of melting below 200 DEG C, therefore, when battery due to inner and or outside stimulation and become high temperature, cause the contraction of organic dividing plate or melting etc., the volume of organic dividing plate changes.Its result, likely causes the short circuit of positive pole and negative pole, sets off an explosion due to electric energy release etc.
In order to solve such problem caused owing to using the organic dividing plate of polyolefin, propose on the organic dividing plate of polyolefin or electrode (negative or positive electrode) superimposed layer contains the layer (perforated membrane) of the non-conductive particles such as inorganic particle.And then, in order to the thermal runaway preventing the abnormal response of battery from causing, the perforated membrane having the polymer beads of the melting containing Yin Re or the polymer beads because of heat swellbility rising is in the electrolytic solution proposed.It is generally acknowledged, when the temperature of secondary cell due to short circuit etc. abnormal rise, there is following function: due to this melting of polymer pellets or swelling and fine space that is that block in perforated membrane, interelectrode ion is stoped to pass through, cause breaking current thus, suppress further temperature to rise (cutting off (shutdown) function).
Such as record in patent documentation 1 a kind of in order to improve fail safe containing heat-resistant resin particulate and the perforated membrane of machine particulate with cutting function.In addition, use ethylene-vinyl acetate polymer is recorded as perforated membrane adhesive.
In patent documentation 2, record a kind of method, described method prevents inorganic filler from the powder falling of perforated membrane by water-dispersible acrylic's polymer beads with hydrophilic radicals such as sulfonic acid is used as adhesive.In addition, recording by further there is crosslinkable groups in water-dispersible acrylic's polymer beads, the tough and tensile and perforated membrane of softness can be had.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-139978 publication
Patent documentation 2: No. WO2009/123168, International Patent Publication
Summary of the invention
The problem that invention will solve
But, according to the research of the present inventor, in patent documentation 1 record perforated membrane due to by ethylene-vinyl acetate polymer be used as adhesive, therefore, dispersiveness for the formation of the heat-resistant resin particulate in the slurry of this perforated membrane and organic fine particles is insufficient, the lack of homogeneity of perforated membrane.Its result, cannot make perforated membrane have sufficient intensity and cutting function sometimes.In addition, known, although the excellent dispersion of the inorganic filler in the perforated membrane perforated membrane slurry recorded in patent documentation 2, but in as the acrylic polymer particles of adhesive containing hydrophilic radical and crosslinkable groups, have and there is mutually reactive functional group, therefore, there is the tendency causing cross-linking reaction in slurry manufacturing process.Therefore, the screening characteristics passing slurry in time becomes unstable, and as a result, the uniformity of perforated membrane and intensity become insufficient sometimes.
Therefore, the object of the invention is to, a kind of secondary cell perforated membrane slurry manufacture using the excellent dispersion of screening characteristics and non-conductive particle is provided, the cycle characteristics of the secondary cell obtained can be improved and uniformity and the high secondary cell perforated membrane of intensity.In addition, its object is to, electrode for secondary battery and secondary battery separator that a kind of cutting function is good are provided.
Therefore, the present inventor etc. concentrate on studies, and found that, by respectively to importing sulfonic group and epoxy radicals in acrylic polymer particles and their material blended being used as adhesive, can improve uniformity and the intensity of perforated membrane.In brief, by using specific adhesive, the cross-linking reaction in slurry manufacturing process can be suppressed, the thickening etc. of slurry can be reduced.Therefore, the dispersiveness of the non-conductive particle in perforated membrane slurry and the screening characteristics of perforated membrane slurry can be improved, uniformity and the much higher pore membrane of intensity can be obtained.In addition, the present inventor finds, by the screening characteristics of the dispersiveness and perforated membrane slurry of improving the non-conductive particle in perforated membrane slurry, except the productivity ratio of perforated membrane, uses the cycle characteristics of the secondary cell of this perforated membrane to be also improved.
For the method for dealing with problems
As described below by the purport of the present invention solved for the purpose of such problem.
(1) a secondary cell perforated membrane slurry, it comprises and forms containing the non-conductive particle of organic macromolecule, adhesive and solvent,
This adhesive contains:
There is sulfonic acrylic polymer particles A, and
There is the acrylic polymer particles B of epoxy radicals.
(2) the secondary cell perforated membrane slurry Gen Ju (1), wherein,
Relative to all solids composition 100 quality %, described non-conductive particle containing ratio be 70 ~ 97 quality %, described adhesive containing ratio be 0.5 ~ 20 quality %.
(3) according to (1) or the secondary cell perforated membrane slurry described in (2), wherein,
Described acrylic polymer particles A and described acrylic polymer particles B forms containing (methyl) acrylonitrile monomer unit and (methyl) acrylate monomeric units.
(4) the secondary cell perforated membrane slurry Gen Ju (3), wherein,
In described acrylic polymer particles A and described acrylic polymer particles B, (methyl) acrylonitrile monomer unit in polymer beads containing ratio be 2.5 ~ 40 quality %, (methyl) acrylate monomeric units in polymer beads containing ratio be 60 ~ 97.5 quality %.
(5) according to the secondary cell perforated membrane slurry according to any one of (1) ~ (4), wherein,
Described acrylic polymer particles A is 0.3 ~ 3 relative to the weight ratio (acrylic polymer particles A/ acrylic polymer particles B) of described acrylic polymer particles B.
(6) according to the secondary cell perforated membrane slurry according to any one of (1) ~ (5), wherein,
In described acrylic polymer particles A sulfonic containing ratio be 0.04 ~ 5.8 quality %, the epoxy radicals in described acrylic polymer particles B containing ratio be 0.03 ~ 3.0 quality %.
(7) according to the secondary cell perforated membrane slurry according to any one of (1) ~ (6), wherein,
In described adhesive, the sulfonic group in described acrylic polymer particles A is 0.2 ~ 3 relative to the weight ratio (sulfonic group/epoxy radicals) of the epoxy radicals in described acrylic polymer particles B.
(8) according to the secondary cell perforated membrane slurry according to any one of (1) ~ (7), wherein,
When heating with programming rate 10 DEG C/min under nitrogen atmosphere with thermobalance, the temperature that the loss of weight ratio of described non-conductive particle reaches 10 quality % is more than 250 DEG C,
The average grain diameter of this non-conductive particle is 0.1 ~ 2.0 μm,
The average circularity of this non-conductive particle is 0.900 ~ 0.995.
(9) a secondary cell perforated membrane, it is by being formed as membranaceous and dry and obtain by the secondary cell perforated membrane slurry according to any one of above-mentioned (1) ~ (8).
(10) electrode for secondary battery, it comprises:
Collector body,
Electrode active material layer, it is attached to this collector body and contains electrode active material and binding agent for electrode, and
Be stacked in the secondary cell perforated membrane described in (9) on this electrode active material layer surface.
(11) secondary battery separator, it comprises:
Organic dividing plate,
Be stacked in the secondary cell perforated membrane described in (9) on this organic dividing plate.
(12) secondary cell, it comprises:
Positive pole, negative pole, organic dividing plate and electrolyte, wherein,
Any superimposed layer in described positive pole, negative pole and organic dividing plate has the secondary cell perforated membrane described in (9).
(13) manufacture method for secondary cell perforated membrane, it comprises:
Basis material is coated with the secondary cell perforated membrane slurry according to any one of above-mentioned (1) ~ (8), then carries out dry operation.
Invention effect
According to the present invention, a kind of secondary cell perforated membrane slurry can be provided, described secondary cell perforated membrane slurry by the adhesive containing non-conductive particle and characteristic composition, thus for the manufacture of uniformity and excellent strength, the secondary cell perforated membrane that can be conducive to the cycle characteristics of secondary cell.In addition, the dispersiveness of this perforated membrane slurry and screening characteristics excellent.And then, by the secondary cell perforated membrane of this perforated membrane slurry manufacture will be used to be stacked on the surface of electrode or organic dividing plate, prevent the disengaging of non-conductive particle and electrode active material (powder falling (powder fall Chi)) and cutting function (reliability) excellent.
Embodiment
Below, (1) of the present invention secondary cell perforated membrane slurry, (2) secondary cell perforated membrane, (3) electrode for secondary battery, (4) secondary battery separator and (5) secondary cell are described successively.
(1) secondary cell perforated membrane slurry
Secondary cell perforated membrane slurry of the present invention (following, be sometimes expressed as " perforated membrane slurry ".) be slurry for the formation of secondary cell perforated membrane described later.Perforated membrane slurry contains the adhesive of non-conductive particle and characteristic composition, is dispersed in as this non-conductive particle of solid constituent, this adhesive and arbitrary uniform composition in solvent described later.
(non-conductive particle)
Organic polymer is contained for non-conductive particle of the present invention.In the present invention, by using containing the non-conductive particle of organic macromolecule, can reduce and cause the pollution of dysgenic metal (below, to be sometimes expressed as " metal impurities " to the performance of secondary cell.), and the manufacturing cost of secondary cell perforated membrane slurry can be suppressed.
Non-conductive particle is preferably containing divinylbenzene monomers unit.The ratio that contains of the divinylbenzene monomers unit of the total monomer weight in non-conductive particle is preferably 20 ~ 80 quality %, is more preferably 25 ~ 70 quality %, is particularly preferably 30 ~ 60 quality %.By the ratio that contains of divinylbenzene monomers unit is set to above-mentioned scope, the crosslink density of non-conductive particle uprises, and thus, the thermal endurance of non-conductive particle improves, and the reliability of the secondary cell perforated membrane obtained also improves.
Non-conductive particle is preferably further containing vinyl xylene, ethyl vinyl benzene monomeric unit.The ratio that contains of the vinyl xylene, ethyl vinyl benzene monomeric unit of the total monomer weight in non-conductive particle is preferably 3.2 ~ 48 quality %, is more preferably 10 ~ 40 quality %.By the ratio that contains of vinyl xylene, ethyl vinyl benzene monomeric unit is set to above-mentioned scope, become good with the caking property of adhesive described later, and the flexibility of the secondary cell perforated membrane obtained becomes good.In addition, when this secondary cell perforated membrane is stacked in electrode made electrode for secondary battery, the disengaging (powder falling) of electrode active material can be prevented.Its result, employs the cycle characteristics that the secondary cell display of this secondary cell perforated membrane is excellent.
Divinylbenzene monomers unit contained in non-conductive particle and the content ratio (divinylbenzene/vinyl xylene, ethyl vinyl benzene) of vinyl xylene, ethyl vinyl benzene monomeric unit are preferably 1.0 ~ 5.25, are more preferably 1.25 ~ 5.00, are particularly preferably 1.25 ~ 4.75.By the content ratio of divinylbenzene monomers unit contained in non-conductive particle and vinyl xylene, ethyl vinyl benzene monomeric unit is set to above-mentioned scope, the crosslink density of non-conductive particle uprises, and therefore, the thermal endurance of non-conductive particle improves.Its result, the flexibility of the secondary cell perforated membrane obtained and intensity improve.In addition, when making electrode for secondary battery, the disengaging (powder falling) of electrode active material can be prevented, therefore, employing the cycle characteristics that the secondary cell display of this secondary cell perforated membrane is excellent.
Non-conductive particle, except above-mentioned 2 kinds of monomeric units, preferably contains the monomer of polar functionalities.
The monomer of polar functionalities be in the molecular structure containing polar group and can with the monomer of divinylbenzene and vinyl xylene, ethyl vinyl benzene copolymerization.Polar group refers to the functional group can dissociated in water or the functional group with polarization, specifically, can enumerate: carboxyl, sulfonic group, hydroxyl, amide groups, cationic groups, cyano group, epoxy radicals etc.
As carboxylic monomer, can enumerate: monocarboxylic acid, dicarboxylic acids, dicarboxylic anhydride and their derivative etc.
As monocarboxylic acid, can enumerate: acrylic acid, methacrylic acid, crotonic acid, 2-ethylacrylic acid, iso-crotonic acid, α-acetoxypropen acid, β-trans-aryloxy group acrylic acid, α-chloro-β-E-methoxy acrylic acid, β-diaminourea acrylic acid etc.
As dicarboxylic acids, can enumerate: maleic acid, fumaric acid, itaconic acid, citraconic acid, dimethyl maleic acid, phenyl maleic acid, chloromaleic acid, dichloro-maleic acid and fluoro maleic acid etc.
As dicarboxylic anhydride, can enumerate: maleic anhydride, acrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride etc.
As dicarboxylic acid derivatives, can enumerate: the maleates such as methyl allyl ester, maleic acid diphenyl ester, maleic acid nonyl ester, maleic acid decyl ester, maleic acid dodecyl ester, maleic acid stearyl and maleic acid fluoroalkyl ester.
As containing sulfonic monomer, can enumerate: vinyl sulfonic acid, methyl ethylene sulfonic acid, (methyl) allyl sulphonic acid, styrene sulfonic acid, (methyl) acrylic acid-2-sulfonic acid, 2-acrylamide-2-methyl propane sulfonic, 3-allyl oxygen-2-hydroxy-propanesulfonic acid etc.
As the monomer of hydroxyl, can enumerate: the ethene unsaturated alcohols such as (methyl) allyl alcohol, 3-butene-1-ol, 5-hexen-1-ol; The chain triacontanol ester class of the ethene unsaturated carboxylic acids such as 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, maleic acid two-2-hydroxy methacrylate, maleic acid two-4-hydroxybutyl, itaconic acid two-2-hydroxy propyl ester; General formula CH 2=CR 1-COO-(C nh 2no) m(m represents that integer, the n of 2 ~ 9 represent the integer of 2 ~ 4 to-H, R 1represent hydrogen or methyl) shown in PAG and (methyl) acrylic acid ester class; List (methyl) esters of acrylic acid of the dihydroxy ester of the dicarboxylic acids such as 2-hydroxyethyl-2 '-(methyl) acryloxy phthalic acid ester, 2-hydroxyethyl-2 '-(methyl) acryloxy succinate; The vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ethers; List (methyl) allyl ether series of the aklylene glycols such as (methyl) pi-allyl-2-hydroxyethyl ether, (methyl) pi-allyl-2-hydroxypropyl ether, (methyl) pi-allyl-3-hydroxypropyl ether, (methyl) pi-allyl-2-hydroxybutyl ether, (methyl) pi-allyl-3-hydroxybutyl ether, (methyl) pi-allyl-4-hydroxybutyl ether, (methyl) pi-allyl-6-hydroxyl hexyl ether; Polyether polyols (methyl) the monoallyl ethers such as diethylene glycol list (methyl) allyl ether, DPG list (methyl) allyl ether; The halogen of (gathering) aklylene glycol and list (methyl) allyl ethers of hydroxyl substituent such as glycerine list (methyl) allyl ether, (methyl) pi-allyl-2-chloro-3-hydroxyl propyl ether, (methyl) pi-allyl-2-hydroxyl-3-chloropropyl ether; List (methyl) allyl ether of the polyhydric phenols such as eugenol, isoeugenol and halogen substituents thereof; (methyl) allyl sulfide ethers etc. of the aklylene glycols such as (methyl) pi-allyl-2-hydroxyethyl thioether, (methyl) pi-allyl-2-hydroxypropyl thioether.
As the monomer of amide-containing, can enumerate: acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide etc.
As the monomer of cation group, can enumerate: (methyl) acrylate, (methyl) acrylate propyl ester etc.
As the monomer of cyano-containing, can enumerate: the acrylonitrile such as acrylonitrile, methacrylonitrile compound.
As the monomer containing epoxy radicals, can enumerate: glycidyl acrylate, glycidyl methacrylate etc.
As the salt of the monomer of carboxylic monomer, monomer, the monomer of amide-containing, the group monomer of cation and cyano-containing containing sulfonic monomer, hydroxyl, can enumerate: the alkali metal salt such as sodium salt, sylvite be made up of above-named monomer and the suitable ion that can combine with them; The alkali salt such as calcium salt, magnesium salts; The organic amine salts etc. such as ammonium salt, monoethanolamine salt, triethanolamine salt.
As the monomer of polar functionalities, the monomer of preferred carboxylic monomer, amide-containing, particularly preferably acrylic acid, methacrylic acid, itaconic acid, acrylamide.
The ratio that contains of the monomer of the polar functionalities of the total monomer weight in non-conductive particle is preferably 0.05 ~ 4 quality %, is more preferably 0.1 ~ 3 quality %, is particularly preferably 0.2 ~ 2 quality %.If not the monomer of the polar functionalities of the total monomer weight in conductive particle is above-mentioned scope, then excellent dispersion containing ratio, and the water content of non-conductive particle surface is few, therefore, the cycle characteristics that display is excellent.
Non-conductive particle, except above-mentioned 3 kinds of monomeric units, also can contain arbitrary monomeric unit.As arbitrary monomer, can enumerate: polynary (methyl) acrylate compounds, aromatic mono-vinyl based compound, (methyl) acrylate monomer, conjugate diene monomer, vinyl ester compound, alpha-olefin compound.In non-conductive particle, these monomers can contain two or more.
As polynary (methyl) acrylate compounds, can enumerate: polyethyleneglycol diacrylate, 1,3-butanediol diacrylate, 1,6-hexanediyl ester, neopentylglycol diacrylate, polypropyleneglycol diacrylate, 2,2 '-bis-(4-acryloxy propoxyphenyl) propane, 2, the diacrylate compounds such as 2 '-bis-(4-acryloxy diethoxy phenyl) propane; The triacrylate compound such as trimethylolpropane triacrylate, methylolethane triacrylate, tetramethylol methane triacrylate; The tetra-acrylate compound such as tetramethylol methane tetraacrylate; Ethylene glycol dimethacrylate, dimethacrylate, TEGDMA, polyethylene glycol dimethacrylate, 1,3-butanediol dimethylacrylate, 1,4-butanediol dimethylacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol dimethacrylate, dipropylene, polypropylene glycol dimethacrylate, 2, the dimethacrylated compounds such as 2 '-bis-(4-methacryloxy diethoxy phenyl) propane; The trimethyl acrylic ester compounds etc. such as trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methacrylate.Wherein, preferably ethylene glycol dimethacrylate or trimethylol-propane trimethacrylate is used.
As aromatic mono-vinyl based compound, can enumerate: styrene, AMS, fluorostyrene, vinylpyridine etc.
As acrylate monomer, can enumerate: butyl acrylate, 2-ethylhexyl ethyl propylene acid esters, acrylic acid N, N '-dimethyl amino-ethyl ester etc.
As methacrylate monomers, can enumerate: butyl methacrylate, 2-Ethylhexyl Methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid N, N '-dimethyl aminoethyl methyl ester etc.
As conjugate diene monomer, can enumerate: butadiene, isoprene etc.
As vinyl ester compound, can enumerate: vinylacetate etc.
As alpha-olefin compound, can enumerate: 4-methyl-1-pentene etc.
Above-mentioned arbitrary monomer can be used alone wantonly a kind or combinationally use two or more.In above-mentioned arbitrary monomer, particularly consider from the reactive viewpoint with divinylbenzene and vinyl xylene, ethyl vinyl benzene, optimization styrene, methyl methacrylate or their combination.
The ratio that contains of the arbitrary monomeric unit of the total monomer weight in non-conductive particle is preferably 3 ~ 80 quality %, is more preferably 4 ~ 70 quality %, is particularly preferably 5 ~ 60 quality %.Particularly when containing styrene and/or methyl methacrylate as arbitrary monomer, its preferably containing ratio with the monomer total amount forming non-conductive particle for benchmark is 4.5 ~ 76.5 quality %.When containing both styrene and methyl methacrylate, preferably their total content is this scope.By styrene and/or methyl methacrylate be set to below 76.5 quality % containing ratio, the thermal endurance of non-conductive particle can be improved, the thermal endurance of perforated membrane can be improved, and then the generation of short circuit of battery under high temperature can be reduced.On the other hand, by the ratio that contains of styrene and/or methyl methacrylate is set to more than 4.5 quality %, can prevents the dispersiveness of non-conductive particle from reducing, improving porous film strength, and can also film uniformity be obtained.
(manufacture method of non-conductive particle)
The manufacture method of non-conductive particle is not particularly limited, following method can be enumerated: will monomer and other the arbitrary component dissolves as required of non-conductive particle be formed or be scattered in decentralized medium, by emulsion polymerization or soap-free polymerization method, be polymerized in this dispersion liquid.
In emulsion polymerisation, from the viewpoint of the particle diameter obtaining expecting and average circularity, preferably multiple stage polymerization is divided into carry out.Such as, forming seeding polymerization composition granule by first the part of monomer forming non-conductive particle being carried out polymerization, next, making other monomer of this seed polymer particulate absorbent, be polymerized in this condition, non-conductive particle (seeded polymerization) can be manufactured.And then when forming seeding polymerization composition granule, polymerization can be further divided into multiple stage carries out.
More specifically, a part for the monomer forming non-conductive particle such as can be used to form seeding polymerization composition granule A, other monomer of this seeding polymerization composition granule A and the non-conductive particle of formation is used to form the seeding polymerization composition granule B with larger particle diameter, and then, use the remaining monomer of this seeding polymerization composition granule B and the non-conductive particle of formation and other arbitrary composition as required to form the non-conductive particle with Large stone further.
As mentioned above, form seeding polymerization composition granule by the reaction in 2 stages, then form non-conductive particle further, obtain while there is Absorbable organic halogens thus the advantage of particle diameter and the average circularity expected.Now, the monomer of the polar functionalities formed in the monomer of non-conductive particle part or all (being preferably all) is used the stability guaranteeing particle when forming seeding polymerization composition granule A and seeding polymerization composition granule B, therefore preferably.And then, now, as the monomer for the formation of seeding polymerization composition granule A, be used as the styrene of arbitrary monomer owing to guaranteeing the absorbability of seed polymer particulate absorbent monomer when forming seeding polymerization composition granule B and non-conductive particle, therefore preferably.
Owing to also comprising the situation being as above divided into multiple stage to carry out being polymerized, therefore, form the monomer of non-conductive particle when being polymerized, its whole monomer also can not be formed into the state of mixture.When polymerization is divided into multiple stage to carry out, the composition of the monomer of the polymerized unit from the non-conductive particle of formation preferably in the non-conductive particle finally obtained meets the ratio of components of the monomer of the non-conductive particle of above-mentioned formation.
As the medium of the polymerization of the monomer for forming non-conductive particle, can enumerate: water, organic solvent and their mixture.As organic solvent, can use and inertia is combined into for radical polymerization and the solvent that can not suppress the polymerization of monomer.As the concrete example of organic solvent, can enumerate: ketone and their mixtures such as ester class, cyclohexanone such as the alcohols such as methyl alcohol, ethanol, propyl alcohol, cyclohexanol, octanol, dibutyl phthalate, dioctyl phthalate.The medium of the water-baseds such as water preferably can be used to carry out the emulsion polymerisation as polymerization as decentralized medium.
With regard to the ratio of their amount when reacting with regard to making seeding polymerization composition granule and monomer, relative to seeding polymerization composition granule 1 mass parts, the use amount of monomer is preferably 2 ~ 19 mass parts, is more preferably 3 ~ 16 mass parts, is more preferably 4 ~ 12 mass parts further.By being more than 2 mass parts by the use amount of the monomer relative to seeding polymerization composition granule 1 mass parts, mechanical strength and the thermal endurance of the non-conductive particle obtained can be improved.In addition, by being below 19 mass parts by the use amount of the monomer relative to seeding polymerization composition granule 1 mass parts, seeding polymerization composition granule can absorb monomer efficiently, therefore, can will not remained less scope by the amount of monomer of seed polymer particulate absorbent.In addition, due to the control of the particle diameter of non-conductive particle can be carried out well, therefore, can prevent that there is the big particle of wide in range domain size distribution and a large amount of molecules.
As the concrete operation of polymerization, have relative to the water-borne dispersions of seeding polymerization composition granule once drop into monomer method, carry out polymerization and separate or add continuously the method for monomer.Preferred polymeric be initiated and produce in fact in seeding polymerization composition granule crosslinked before make seed polymer particulate absorbent monomer.
If add monomer after the mid-term of polymerization, then because monomer is not by seed polymer particulate absorbent, therefore, a large amount of molecule that produces makes polymerization stability be deteriorated, and sometimes cannot maintain polymerization reaction.Therefore, preferably reach relative to seeding polymerization the composition granule whole monomer of interpolation or polymerisation conversion before polymerization causes the interpolation terminating whole monomer before about 30%.In the water-borne dispersions of seeding polymerization composition granule, add monomer stir before causing particularly preferably in polymerization, make initiated polymerization after monomer described in seed polymer particulate absorbent.
In the reaction system of polymerization except the monomer forming non-conductive particle and decentralized medium, any composition can be added.Specifically, the compositions such as polymerization initiator, surfactant, suspension protective agent can be added.As polymerization initiator, general water miscible radical polymerization initiator or oil-soluble radical polymerization initiator can be used, but never by the monomer of seed polymer particulate absorbent initiated polymerization in aqueous phase few in consider, preferably use water miscible radical polymerization initiator.As water miscible radical polymerization initiator, can enumerate: the redox series initiators be combined to form of potassium peroxydisulfate, sodium peroxydisulfate, hydrogen phosphide cumene, hydrogen peroxide or above-mentioned water soluble starter or the reducing agent such as oil-soluble initiator described later and sodium hydrogensulfite.In addition, as oil-soluble radical polymerization initiator, can enumerate: benzoyl peroxide, α, α '-azodiisobutyronitrile, peroxidating (2 ethyl hexanoic acid) tert-butyl ester, 3,5,5-trimethyl acetyl base peroxide etc.In oil-soluble radical polymerization initiator, preferably can use peroxidating (2 ethyl hexanoic acid) tert-butyl ester.In addition, in the polymerization, if add the water miscible polymerization inhibitors such as potassium bichromate, iron chloride, quinhydrones on a small quantity, then the generation of molecule can be suppressed, therefore preferably.
As surfactant, common surfactant can be used, can illustrate: the anion system emulsifying agents such as the formaldehyde condensation products of such as neopelex, NaLS, dialkyl sodium sulfosuccinate, naphthalene sulfonic acids.And then, also can combinationally use the nonionic system surfactants such as ethylene nonyl phenyl ether, polyethyleneglycol hard acid esters, sorbitan list hard acid esters.As the protective agent that preferably suspends, can enumerate: polyvinyl alcohol, carboxymethyl cellulose, Sodium Polyacrylate or micropowder inorganic compound etc.
(proterties of non-conductive particle)
Shape for non-conductive particle of the present invention is spherical, needle-like, bar-shaped, fusiform, tabular etc., is not particularly limited, but preferably spherical, needle-like, fusiform.In addition, as non-conductive particle, also porous particles can be used.Relative to all solids composition 100 quality % of perforated membrane slurry, the ratio that contains of non-conductive particle is preferably 70 ~ 97 quality %, is more preferably 80 ~ 95 quality %, is particularly preferably 85 ~ 95 quality %.Be set to above-mentioned scope by the ratio that contains of the non-conductive particle by all solids composition 100 quality % relative to perforated membrane slurry, the perforated membrane showing high thermal stability can be obtained.In addition, the non-conductive particle that can be inhibited from the disengaging (powder falling) of perforated membrane and the perforated membrane of display high strength, can prevent the reduction of the battery behaviors such as cycle characteristics simultaneously.
From the viewpoint of giving thermal endurance to perforated membrane and improving the reliability of electrode for secondary battery described later and secondary battery separator, preferred non-conductive particle has high-fire resistance.Specifically, the temperature that the loss of weight ratio of non-conductive particle when heating with programming rate 10 DEG C/min in the thermogravimetric analyses under blanket of nitrogen reaches 10 quality % is preferably more than 250 DEG C, is more preferably more than 300 DEG C, is particularly preferably more than 360 DEG C.On the other hand, the upper limit of this temperature is not particularly limited, and can be set to such as less than 450 DEG C.
In the present invention, as non-conductive particle, preferably use the non-conductive particle that the content of metal impurities is below 100ppm.If use the non-conductive particle more containing metal impurities or metal ion, then in perforated membrane slurry, above-mentioned metal impurities or digestion of metallic ion, it causes polymer in perforated membrane slurry and ionomer, perforated membrane slurry condenses, and result causes the porousness of perforated membrane to reduce.Therefore, the multiplying power property (output characteristic) of the secondary cell of this perforated membrane is likely used to be deteriorated.As above-mentioned metal, least preferred containing particularly Ca, Co, Cu, Fe, Mg, Ni, Zn and Cr etc.Therefore, as the tenor in non-conductive particle, be preferably below 100ppm with the total amount of these metal ions, more preferably below 50ppm.Above-mentioned content is fewer, more not easily causes the deterioration of battery behavior.Metal simple-substance beyond non-conductive particle or metal ion is referred at these said " metal impurities ".The content of the metal impurities in non-conductive particle can use ICP (inductively coupled plasma (InductivelyCoupled Plasma)) to measure.
Average grain diameter for non-conductive particle of the present invention is preferably 0.1 ~ 2 μm, is more preferably 0.1 ~ 1 μm, is particularly preferably 0.1 ~ 0.8 μm.By the average grain diameter of non-conductive particle is set to above-mentioned scope, easily control the dispersity of perforated membrane slurry, therefore, the manufacture of the perforated membrane of uniform specific thickness becomes easy.In addition, the particles filled rate in perforated membrane can be suppressed to uprise, therefore, the ionic conductivity in perforated membrane can be suppressed to reduce, excellent cycle characteristics can be realized.If make the average grain diameter of non-conductive particle be the scope of 0.1 ~ 0.8 μm, then the controlling in the easiness disperse, be coated with, space is excellent, therefore preferably.For average grain diameter, can calculate as follows: carry out electron microscope observation, for more than 100 particles, the longest edge of its particle picture is set to a, most minor face is set to b, calculate (a+b)/2, and obtained by its mean value.
Average circularity for non-conductive particle of the present invention is preferably 0.900 ~ 0.995, is more preferably 0.91 ~ 0.98, is particularly preferably 0.92 ~ 0.97.By the average circularity of non-conductive particle is set to above-mentioned scope, non-conductive particle contact area each other appropriateness can be kept, therefore, porous film strength and thermal endurance can be improved.Its result, can improve the reliability of the secondary cell employing this perforated membrane.
In addition, for the BET specific surface area of non-conductive particle of the present invention from the viewpoint of suppressing the cohesion of non-conductive particle and optimizing the mobility of perforated membrane slurry, specifically, preferably 0.9 ~ 200m 2/ g, is more preferably 1.5 ~ 150m 2/ g.
The domain size distribution of non-conductive particle is preferably 1.00 ~ 1.4, is more preferably 1.00 ~ 1.3, is particularly preferably 1.00 ~ 1.2.By the domain size distribution of non-conductive particle is set to above-mentioned scope, the space specified can be kept between non-conductive particle, therefore, the resistance caused owing to hindering moving of lithium in secondary cell of the present invention can be suppressed to increase.In addition, the domain size distribution of non-conductive particle can use the laser diffraction of Beckman Co., Ltd. to reflect after particle size distribution device (LS230) carries out particle size determination, is obtained by the ratio V/N of the volume average particle size V obtained and number average bead diameter N.
(adhesive)
The acrylic polymer particles B that there is sulfonic acrylic polymer particles A and there is epoxy radicals is contained for adhesive of the present invention.In the present invention, by using the adhesive containing this acrylic polymer particles A and this acrylic polymer particles B, the gelation of perforated membrane slurry can be prevented, therefore, uniform perforated membrane can be formed.
There is sulfonic acrylic polymer particles A form containing having sulfonic monomeric unit.Specifically, it is characterized in that, containing having sulfonic monomeric unit in the polymer as acrylic polymer particles A.
As having sulfonic monomer, can enumerate: vinyl sulfonic acid, methyl ethylene sulfonic acid, (methyl) allyl sulphonic acid, styrene sulfonic acid, (methyl) acrylic acid-2-sulfonic acid, 2-acrylamide-2-methyl propane sulfonic, 3-allyl oxygen-2-hydroxy-propanesulfonic acid, Sodium styrene sulfonate etc.
The ratio that contains with sulfonic monomeric unit in acrylic polymer particles A is preferably 0.3 ~ 10 quality %, is more preferably 1.3 ~ 9 quality %.If in acrylic polymer particles A have sulfonic monomeric unit containing ratio be above-mentioned scope, then can give good caking property to adhesive, non-conductive particle can be suppressed from the disengaging (powder falling) of perforated membrane.
The sulfonic ratio that contains in acrylic polymer particles A is preferably 0.04 ~ 5.8 quality %, is more preferably 0.1 ~ 4 quality %, is particularly preferably 0.5 ~ 3.5 quality %.If sulfonic in acrylic polymer particles A is above-mentioned scope containing ratio, then can prevent the viscosity of perforated membrane slurry from rising, well the screening characteristics of maintenance perforated membrane slurry.In addition, relative to non-conductive particle, there is sufficient cohesive force, and uprise with the reactivity of the epoxy radicals of acrylic polymer particles B described later.And then, improve the dispersiveness of the non-conductive particle in perforated membrane slurry.
Acrylic polymer particles A, except having sulfonic monomeric unit, preferably contains (methyl) acrylonitrile monomer unit further.The ratio that contains of (methyl) acrylonitrile monomer unit in acrylic polymer particles A is preferably 2.5 ~ 40 quality %, is more preferably 3 ~ 37 quality %, is particularly preferably 5 ~ 35 quality %.If (methyl) acrylonitrile monomer unit in acrylic polymer particles A is above-mentioned scope containing ratio, then the intensity of adhesive improves, and therefore, can manufacture the secondary cell with excellent cycle characteristics.
In addition, in the present invention, there is sulfonic acrylic polymer particles A except above-mentioned monomeric unit, preferably further containing (methyl) acrylate monomeric units.The ratio that contains of (methyl) acrylate monomeric units in acrylic polymer particles A is preferably 60 ~ 97.5 quality %, is more preferably 62 ~ 96 quality %, is particularly preferably 65 ~ 95 quality %.If (methyl) acrylate monomeric units in acrylic polymer particles A is above-mentioned scope containing ratio, then adhesive not stripping and show the swellability of the appropriateness to electrolyte in the electrolyte of secondary cell, therefore, the conductibility of lithium ion can be kept well.Its result.The cycle characteristics of secondary cell can be improved.
As (methyl) acrylate monomer, can enumerate: the alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, amyl acrylate, Hexyl 2-propenoate, heptylacrylate, 2-ethyl hexyl acrylate, 2-EHA, acrylic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, lauryl acrylate, n-myristyl base ester, stearyl acrylate ester, methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, Tert-butyl Methacrylate, pentylmethacrylate, hexyl methacrylate, metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, 2-Ethylhexyl Methacrylate, nonyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, methacrylic acid n-tetradecane base ester, the alkyl methacrylates such as stearyl methacrylate.Wherein, carbon number due to the alkyl with non-carbonyl oxygen atoms bond is (methyl) ethyl acrylate of 2 ~ 13, (methyl) n-butyl acrylate, (methyl) 2-EHA, the display of (methyl) lauryl acrylate is stripping and the swelling of the appropriateness of electrolyte is brought thus to the conductibility of lithium ion in the electrolytic solution not, in addition, the cross-linked cohesion causing polymer is difficult in the dispersion of active material, therefore preferably, wherein, it is preferably (methyl) n-butyl acrylate of 4 ~ 10 with the carbon number of the alkyl of non-carbonyl oxygen atoms bond, (methyl) 2-EHA.
And then, acrylic polymer particles A except above-mentioned monomeric unit (there is sulfonic monomeric unit, (methyl) acrylonitrile monomer unit and (methyl) acrylate monomeric units), preferably containing can with other the monomeric unit of their copolymerization.The ratio that contains of other the monomeric unit in acrylic polymer particles A is preferably 0.1 ~ 10 quality %, is more preferably 0.1 ~ 5 quality %.If other the monomeric unit in acrylic polymer particles A is above-mentioned scope containing ratio, then the dispersiveness of particle can not reduce, and can be formed uniformly perforated membrane.
As other monomer, can enumerate: the styrenic monomers such as styrene, chlorostyrene, vinyltoluene, t-butyl styrene, vinyl benzoic acid, vinylbenzoate, vinyl naphthalene, 1-chloro-4-methyl-benzene, AMS, divinylbenzene; Acrylic acid, methacrylic acid, crotonic acid, 2-ethylacrylic acid, iso-crotonic acid, α-acetoxypropen acid, β-trans aryloxy group acrylic acid, α-chloro-β-E-methoxy acrylic acid, β-diaminourea acrylic acid etc. have the ethene system unsaturated carboxylic acid of monocarboxylic acid; Maleic acid, fumaric acid, itaconic acid, citraconic acid, dimethyl maleic acid, phenyl maleic acid, chloromaleic acid, dichloro-maleic acid, fluoro maleic acid and maleate etc. have ethene system unsaturated carboxylic acid and the derivative thereof of dicarboxylic acids; The olefines such as ethene, propylene; The diene monomer such as butadiene, isoprene; The halogen atom such as vinyl chloride, vinylidene chloride monomer; The vinyl esters such as vinylacetate, propionate, vinyl butyrate; The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; The vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, isopropenyl vinyl ketone; NVP, vinylpyridine, vinyl imidazole etc. are containing heterocyclic vinyl compounds; The acid amides such as acrylamide, N hydroxymethyl acrylamide system monomer etc.In addition, acrylic polymer particles A only containing other monomeric unit a kind of, also can contain two or more with arbitrary ratio combine.
The acrylic polymer particles B with epoxy radicals is containing the monomeric unit with epoxy radicals.Specifically, it is characterized in that, containing the monomeric unit with epoxy radicals in the polymer as acrylic polymer particles B.
As the monomer with epoxy radicals, can enumerate: the unsaturated glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, cyclobutenyl glycidyl ether, o-allyl base glycidyl ether; The monoepoxide of the diene such as butadiene monoepoxide, chlorobutadiene monoepoxide, 4,5-epoxy-2-amylenes, 3,4-epoxy-1-VCHs, 1,2-epoxy-5,9-ring 12 carbon diene or polyenoid; The alkenyl epoxides such as 3,4-epoxy-1-butylene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; The glycidyl esters class of the unsaturated carboxylic acids such as the glycidyl esters of glycidyl acrylate, glycidyl methacrylate, crotonic acid ethylene oxidic ester, glycidyl-4-heptenoic acid esters, sorbic acid ethylene oxidic ester, linoleic acid ethylene oxidic ester, glycidyl-pyroterebic acid ester, 3-cyclohexene carboxylate, the glycidyl esters of 4-methyl-3-cyclohexene carboxylate.Wherein, from due to high with the reactivity of sour functional groups, therefore, the caking property of the perforated membrane obtained is high and powder falling is low, the aspect employing the cycle characteristics excellence of the battery of perforated membrane is considered, preferred vinyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, most preferably glycidyl acrylate, glycidyl methacrylate.
The ratio that contains with the monomeric unit of epoxy radicals in acrylic polymer particles B is preferably 0.3 ~ 8 quality %, is more preferably 0.3 ~ 5 quality %.If in acrylic polymer particles B have the monomeric unit of epoxy radicals containing ratio be above-mentioned scope, then can give good caking property to adhesive, non-conductive particle can be suppressed from the disengaging (powder falling) of perforated membrane.
The ratio that contains of the epoxy radicals in acrylic polymer particles B is preferably 0.03 ~ 3.0 quality %, is more preferably 0.1 ~ 2.5 quality %, is particularly preferably 0.1 ~ 1.5 quality %.If the epoxy radicals in acrylic polymer particles B is above-mentioned scope containing ratio, then can prevent the viscosity of perforated membrane slurry from rising and keeping the screening characteristics of perforated membrane slurry well.In addition, uprise with the sulfonic reactivity of above-mentioned acrylic polymer particles A, therefore, porous film strength improves.
Acrylic polymer particles B except the monomeric unit with epoxy radicals, preferably further containing (methyl) acrylonitrile monomer unit, (methyl) acrylate monomeric units and can with other the monomeric unit of their copolymerization.(methyl) acrylonitrile monomer unit in acrylic particles B containing ratio, (methyl) acrylate monomeric units containing ratio and can with other the monomeric unit of their copolymerization containing in ratio and above-mentioned acrylic polymer particles A to contain ratio identical.In addition, each monomer can illustrate the monomer same with the monomer in above-mentioned acrylic polymer particles A.
Acrylic polymer particles A is preferably 0.3 ~ 3 relative to the weight ratio (acrylic polymer particles A/ acrylic polymer particles B) of acrylic polymer particles B, is more preferably 0.4 ~ 3, is particularly preferably 0.5 ~ 2.Be above-mentioned scope by making acrylic polymer particles A relative to the weight ratio of acrylic polymer particles B, the gelation (viscosity rising) of perforated membrane slurry can be prevented, make the screening characteristics of perforated membrane slurry good, the porous film strength obtained improves.
Acrylic polymer particles A and acrylic polymer particles B uses under the state of the solution of the dispersion liquid or dissolving that are scattered in decentralized medium (water or organic solvent) (following, be sometimes designated as " polymer particles dispersion A " and " polymer particles dispersion B ".)。In the present invention, excellent from the viewpoint of the viewpoint of environment, rate of drying is fast, preferably use water is as decentralized medium.In addition, when with an organic solvent as decentralized medium, use the organic solvents such as 1-METHYLPYRROLIDONE (NMP).
When acrylic polymer particles A and acrylic polymer particles B is scattered in decentralized medium with graininess, with the average grain diameter (dispersion particle diameter) preferably 0.05 ~ 0.5 μm of the acrylic polymer particles A of graininess dispersion and acrylic polymer particles B, preferably 0.07 ~ 0.4 μm further, be most preferably preferably 0.1 ~ 0.25 μm.If the average grain diameter of acrylic polymer particles A and acrylic polymer particles B is above-mentioned scope, then the porous film strength obtained and flexibility become good.
When acrylic polymer particles A and acrylic polymer particles B is scattered in decentralized medium with graininess, the solid component concentration of dispersion liquid is generally 15 ~ 70 quality %, preferably 20 ~ 65 quality %, further preferred 30 ~ 60 quality %.If solid component concentration is this scope, then workability when manufacturing perforated membrane slurry is good.
Glass transition temperature (Tg) for acrylic polymer particles A and B of the present invention is preferably-50 ~ 25 DEG C, is more preferably-45 ~ 15 DEG C, is particularly preferably-40 ~ 5 DEG C.Be above-mentioned scope by the Tg of acrylic polymer particles A and acrylic polymer particles B, perforated membrane of the present invention has excellent intensity and flexibility, therefore, can improve the output characteristic of the secondary cell employing this perforated membrane.In addition, the glass transition temperature of acrylic polymer particles A and acrylic polymer particles B can by combining various monomer to adjust.
Manufacture method for acrylic polymer particles A of the present invention and acrylic polymer particles B is not particularly limited, and also can use the either method in solution polymerization process, suspension polymerization, mass polymerization, emulsion polymerization etc.As polymerization reaction, the arbitrary reaction in ionic polymerization, radical polymerization, active free radical polymerization etc. also can be used.As the polymerization initiator for being polymerized; such as lauroyl peroxide, diisopropyl peroxydicarbonate, two-2-ethylhexyl peroxy dicarbonates, tert-Butyl peroxypivalate, 3 can be enumerated; 3; organic peroxide, the α such as 5-trimethyl acetyl base peroxide, azo-compound or ammonium persulfate, the potassium peroxydisulfates etc. such as α '-azodiisobutyronitrile.
For acrylic polymer particles A of the present invention and acrylic polymer particles B preferably in its manufacturing process, the granular metal removal step of granular metal contained in removing polymer particles dispersion A and polymer particles dispersion B obtains.By making in polymer particles dispersion A and polymer particles dispersion B the content of contained granular metal composition be below 10ppm, can prevent between the polymer in perforated membrane slurry through time metal ion crosslinked, prevent viscosity from rising.And then the worry that the self discharge that causes of dissolving/precipitations during internal short-circuit or charging for secondary cell increases is less, the cycle characteristics of battery and fail safe raising.
The method removing granular metal ingredient from polymer particles dispersion A and polymer particles dispersion B in above-mentioned granular metal removal step is not particularly limited, such as, can enumerate: the method for being undertaken by utilizing the filtration of filter removing, the method for being undertaken removing by vibrating screen, the method for being undertaken removing by centrifugation, the method etc. that removes of being undertaken by magnetic force.Wherein, because removing object is metal ingredient, therefore, remove preferably by magnetic force.As the method for being undertaken removing by magnetic force, as long as the method that can remove metal ingredient is just not particularly limited, if consider productivity ratio and removing efficiency, then preferably by configuring magnetic filter to carry out in the manufacture line of acrylic polymer particles A and acrylic polymer particles B.
Manufacture method for adhesive of the present invention is not particularly limited, and can manufacture by mixing above-mentioned polymer particles dispersion A and polymer particles dispersion B.As long as mixing arrangement is just be not particularly limited by the device that polymer particles dispersion A and polymer particles dispersion B mixes equably, such as, can enumerate: the method employing stirring-type, oscillatory type and rotary etc. mixing arrangement.In addition, can enumerate: the method employing the dispersion kneading devices such as homogenizer, ball mill, sand mill, roller mill, planetary stirring machine and planetary mixer.
Acrylic polymer particles A in adhesive is preferably 30 ~ 75 quality % containing ratio, is more preferably 33 ~ 66 quality %, and the acrylic polymer particles B in adhesive is preferably 25 ~ 70 quality % containing ratio, is more preferably 33 ~ 66 quality %.If the acrylic polymer particles A's in adhesive and acrylic polymer particles B is above-mentioned scope containing ratio, then cohesive force is good, and in addition, adhesive can not thickening and disperseing, and therefore, the flatness of perforated membrane is also excellent.
Sulfonic group in acrylic polymer particles A in adhesive is preferably 0.2 ~ 3 relative to the weight ratio (sulfonic group/epoxy radicals) of the epoxy radicals in acrylic polymer particles B, is more preferably 0.3 ~ 3, is particularly preferably 0.3 ~ 2.If the sulfonic group in adhesive is above-mentioned scope relative to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals, then can prevent the gelation of perforated membrane slurry, make the screening characteristics of perforated membrane slurry good, the porous film strength obtained improves.
The average grain diameter of adhesive is preferably 0.05 ~ 0.5 μm, is more preferably 0.07 ~ 0.4 μm, is particularly preferably 0.10 ~ 0.25 μm.Average grain diameter can by obtaining by determination of laser diffraction particle size distribution.By the average grain diameter of adhesive is set to above-mentioned scope, become good with the caking property of non-conductive particle, therefore, the flexibility of the secondary cell perforated membrane obtained improves, and can prevent non-conductive particle from departing from (powder falling) from secondary cell perforated membrane.Its result, employs fail safe and the cycle characteristics of the secondary cell display excellence of this secondary cell perforated membrane.
Relative to all solids composition 100 quality % of perforated membrane slurry, the ratio that contains of adhesive is preferably 0.5 ~ 20 quality %, is more preferably 5 ~ 20 quality %, is particularly preferably 5 ~ 15 quality %.Be above-mentioned scope by what make the adhesive of all solids composition 100 quality % relative to perforated membrane slurry containing ratio, the cohesive force between non-conductive particle can be kept well, improve the flexibility of perforated membrane.In addition, the cycle characteristics of the secondary cell obtained can be improved.
(solvent)
As the solvent for perforated membrane slurry, what also can use in water and organic solvent is any.As organic solvent, can enumerate: the annular aliphatic such as pentamethylene, cyclohexane hydro carbons; Toluene, dimethylbenzene, ethylo benzene etc. are aromatic hydrocarbon based; The ketones such as acetone, ethyl methyl ketone, diisopropyl ketone, cyclohexanone, hexahydrotoluene, ethyl cyclohexane; The chlorine system aliphatic hydrocarbons such as carrene, chloroform, carbon tetrachloride; The ester classes such as ethyl acetate, butyl acetate, gamma-butyrolacton, 6-caprolactone; The nitrile such as acetonitrile, propionitrile (ア シ ロ ニ ト リ Le); The ethers such as oxolane, ethylene glycol diethyl ether: the alcohols such as methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycol monoethyl ether; The amide-type such as 1-METHYLPYRROLIDONE, DMF.
These solvents can be used alone, and also they can be mixed two or more and make mixed solvent to use.Wherein, particularly the excellent dispersion of non-conductive particle, the boiling point low and solvent that volatility is high can remove under low temperature in the short time, therefore preferably.Specifically, preferred acetone, toluene, cyclohexanone, pentamethylene, oxolane, cyclohexane, dimethylbenzene, water or 1-METHYLPYRROLIDONE or their mixed solvent.
(arbitrary composition)
In perforated membrane slurry except mentioned component (non-conductive particle, adhesive and solvent), arbitrary composition can be contained further.As this arbitrary composition, can enumerate: the composition such as the binding agent beyond inorganic particle, dispersant, levelling agent, antioxidant, above-mentioned adhesive, tackifier, defoamer and the electrolysis additive with functions such as electrolyte decomposition suppression.As long as these can not impact cell reaction and just be not particularly limited.
As inorganic particle, the various inorganic particles such as such as aluminium oxide, silica, magnesium oxide, titanium oxide, aluminium nitride, calcirm-fluoride, barium fluoride, talcum, montmorillonite can be used.It not particularly preferably spherical special-shaped particle.Relative to all solids composition 100 quality % of perforated membrane slurry, inorganic particle containing ratio be below 20 quality %, be more preferably below 10 quality %.If inorganic particle be this scope containing ratio, then can obtain intensity by force and the good perforated membrane of the permeability of lithium ion.
As dispersant, Exemplary anions compound, cationic compound, nonionic compound, macromolecular compound.Dispersant can be selected according to the non-conductive particle used.Relative to all solids composition 100 quality % of perforated membrane slurry, dispersant containing ratio preferably not to the scope that battery behavior impacts, be specifically below 10 quality %.If dispersant is this scope containing ratio, then the screening characteristics of perforated membrane slurry of the present invention is good, can obtain uniform perforated membrane.
As levelling agent, can enumerate: the surfactant such as alkyl system surfactant, silicone based surfactants, fluorine system surfactant, metal system surfactant.Relative to all solids composition 100 quality % of perforated membrane slurry, surfactant containing ratio preferably not to the scope that battery behavior impacts, be specifically below 10 quality %.By mixing above-mentioned surfactant, can prevent from repelling when perforated membrane slurry of the present invention is coated on the basis material of regulation (は じ I), the flatness of perforated membrane is improved.
As antioxidant, can enumerate: phenolic compound, hydroquinone compound, organic phosphorus compound, sulphur compound, phenylenediamine compound, polymer-type phenolic compound etc.Polymer-type phenolic compound is the polymer in molecule with phenol structure, weight average molecular weight preferably can be used to be 200 ~ 1000, be preferably the polymer-type phenolic compound of 600 ~ 700.Relative to all solids composition 100 quality % of perforated membrane slurry, antioxidant containing ratio preferably not to the scope that battery behavior impacts, be specifically below 10 quality %.If antioxidant is this scope containing ratio, then the cycle life of battery is excellent.
As the binding agent beyond above-mentioned adhesive, the polytetrafluoroethylene (PTFE), Kynoar (PVDF), polyacrylic acid derivative, HPAM Degraded Bacteria, soft polymer etc. that use in binding agent for electrode described later can be used.Relative to all solids composition 100 quality % of perforated membrane slurry, the binding agent beyond above-mentioned adhesive containing ratio be below 10 quality %.If binding agent is this scope containing ratio, then the adaptation of perforated membrane of the present invention and electrode active material layer described later, organic dividing plate is good.
As tackifier, the cellulose-based polymer such as carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose and these ammonium salt and alkali metal salt can be enumerated; (modification) poly-(methyl) acrylic acid and these ammonium salt and alkali metal salt; The polyvinyl alcohols such as the copolymer of the copolymer of (modification) polyvinyl alcohol, acrylic acid or acrylates and vinyl alcohol, maleic anhydride or maleic acid or fumaric acid and vinyl alcohol; Polyethylene glycol, poly(ethylene oxide), PVP, modified polyacrylic acid, oxidized starch, starch phosphate, casein, various modified starch, acrylonitrile-butadiene copolymer hydride etc.Relative to all solids composition 100 quality % of perforated membrane slurry, tackifier containing ratio preferably not to the scope that battery behavior impacts, be specifically below 10 quality %.If tackifier is this scope containing ratio, then the adaptation of the screening characteristics of perforated membrane slurry of the present invention and perforated membrane of the present invention and electrode active material layer described later, organic dividing plate is good.In the present invention, " (modification) gathers " refers to " unmodified poly-" or " modification gathers ", and " (methyl) acrylic acid " refers to " acrylic acid " or " methacrylic acid ".
As defoamer, use metal soap, polysiloxane-based, polyethers, higher alcohols, perfluoroalkyl class etc.Relative to all solids composition 100 quality % of perforated membrane slurry, defoamer containing ratio preferably not to the scope that battery behavior impacts, be specifically below 10 quality %.By mixture foam killer, the froth breaking operation of adhesive can be shortened.
Electrolysis additive can be used in the vinylene carbonate etc. used in electrode slurry described later and in electrolyte.Relative to all solids composition 100 quality % of perforated membrane slurry, electrolysis additive containing ratio preferably not to the scope that battery behavior impacts, be specifically below 10 quality %.By mixed electrolytic solution additive, the cycle life of battery is excellent.
In addition, can enumerate: the nanoparticles such as aerosil and gaseous oxidation aluminium.By mixing above-mentioned nanoparticle, the thixotropy of perforated membrane slurry can be controlled, and then, the levelability of the perforated membrane obtained thus can be improved.
Relative to all solids composition 100 quality % of perforated membrane slurry, the summation containing ratio of above-mentioned arbitrary composition is preferably below 40 quality %, is more preferably below 20 quality %.But, at above-mentioned non-conductive particle, adhesive and arbitrary composition (wherein, do not comprise inorganic particle, binding agent) summation lower than 100 quality % when, convenient increment as any composition binding agent containing ratio, can composition be obtained.
As long as the solid component concentration of perforated membrane slurry be can carry out the coating of this slurry, the degree of dipping and the viscosity with mobility are just not particularly limited, and are generally speaking about 10 ~ 50 quality %.
Composition beyond solid constituent is the composition volatilized by the operation of drying, except above-mentioned solvent, such as, dissolves or disperse their medium when being also included in the preparation of non-conductive particle and adhesive and adding.
The manufacture method of secondary cell perforated membrane slurry is not particularly limited, by mixing above-mentioned non-conductive particle, adhesive, solvent and the arbitrary one-tenth that adds as required assigns to manufacture.In the present invention, by using and mixing mentioned component (non-conductive particle, adhesive, solvent and the arbitrary composition added as required), have nothing to do with mixed method and order by merging, all can obtain the perforated membrane slurry of non-conductive particle high degree of dispersion.Mixing arrangement can use the mixing arrangement same with the mixing arrangement of the manufacture for above-mentioned adhesive.Wherein, ball mill, roller mill, the contour dispersal device of Filmix that can apply high dispersive and shear particularly preferably is used.
The viscosity of perforated membrane slurry, from the viewpoint of even application, slurry ageing stability, is preferably 10 ~ 10,000mPas, more preferably 50 ~ 500mPas.Above-mentioned viscosity be use Brookfield viscometer 25 DEG C, measure under the condition of revolution 60rpm time value.
(2) secondary cell perforated membrane
Secondary cell perforated membrane of the present invention (following, be sometimes expressed as " perforated membrane ".) be that above-mentioned secondary cell perforated membrane slurry is formed as membranaceous and carries out drying.
Perforated membrane is stacked on organic dividing plate or electrode and uses or use as organic dividing plate itself.
The manufacture method > of < secondary cell perforated membrane
As the method manufacturing perforated membrane of the present invention, can enumerate: the perforated membrane slurry containing above-mentioned non-conductive particle, adhesive, solvent and arbitrary composition is coated on the basis material (positive pole, negative pole or organic dividing plate) of regulation by (I), then carries out dry method; (II) by the perforated membrane impregnating slurry containing above-mentioned non-conductive particle, adhesive, solvent and arbitrary composition after basis material (positive pole, negative pole or organic dividing plate), carried out dry method; (III) the perforated membrane slurry containing above-mentioned non-conductive particle, adhesive, solvent and arbitrary composition is coated on stripping film carries out film forming, the perforated membrane obtained is transferred in the method on the basis material (positive pole, negative pole or organic dividing plate) of regulation.Wherein, (I) perforated membrane slurry is coated on basis material (positive pole, negative pole or organic dividing plate), then carries out the thickness that dry method easily controls perforated membrane, therefore most preferably.
Perforated membrane of the present invention is by the method manufacture of above-mentioned (I) ~ (III), and below, the manufacture method detailed to it is described.
In the method for (I), the basis material (positive pole, negative pole or organic dividing plate) perforated membrane slurry being coated on regulation is gone up and carries out drying, manufactures perforated membrane of the present invention thus.
The method that this slurry is coated on basis material is not particularly limited, such as, can enumerates: the methods such as scraper for coating method, reverse roll method, directly roller method, intagliotype, extrusion, spread coating.Wherein, from the viewpoint of obtaining uniform perforated membrane, preferred intagliotype.
As drying means, can enumerate: utilize the seasoning that the drying of such as warm air, hot blast, low wet wind, vacuumize, utilization (far) infrared ray or electron beam etc. irradiate.Baking temperature can change according to the kind of the solvent used.In order to completely except desolventizing, such as, when the solvent using the volatility such as 1-METHYLPYRROLIDONE low, preferably carry out drying with under high temperature more than 120 DEG C of the drying machine of blast type.On the contrary, when the solvent using volatility high, also drying can be carried out under the low temperature below 100 DEG C.When organic dividing plate described later forms perforated membrane, owing to needing to carry out drying with not causing the contraction of organic dividing plate, therefore, the drying under the low temperature preferably below 100 DEG C.
In the method for (II), perforated membrane impregnating slurry is carried out drying in basis material (positive pole, negative pole or organic dividing plate), manufactures perforated membrane of the present invention thus.The method of this impregnating slurry in basis material is not particularly limited, such as can by carrying out dip coated to flood with dip coater etc.
As drying means, the method identical with the drying means in the method for above-mentioned (I) can be enumerated.
In the method for (III), perforated membrane slurry to be coated on stripping film and to carry out film forming, manufacturing the perforated membrane be formed on stripping film.Then, the perforated membrane obtained is transferred on basis material (positive pole, negative pole or organic dividing plate).
As coating process, the method identical with the coating process in the method for above-mentioned (I) can be enumerated.Printing transferring method is not particularly limited.
(I) perforated membrane obtained in the method for ~ (III) then also can use moulding press or roll squeezer etc. to improve the adaptation of basis material (positive pole, negative pole or organic dividing plate) and perforated membrane by pressurized treatments as required.But now, if excessively carry out pressurized treatments, then the voidage of perforated membrane is impaired sometimes, therefore, suitable controlled pressure and pressing time.
The thickness of perforated membrane is not particularly limited, can according to the purposes of perforated membrane or the suitable setting of application, if cross thin, then cannot form uniform film, on the contrary, if blocked up, the capacity (capacity) of the unit volume (weight) then in battery reduces, therefore, preferably 0.5 ~ 50 μm, more preferably 0.5 ~ 10 μm.
Perforated membrane of the present invention, at the surface filming of basis material (positive pole, negative pole or organic dividing plate), is especially preferably used as diaphragm or the dividing plate of electrode active material layer described later.Perforated membrane of the present invention can film forming on the arbitrary surfaces in the positive pole of secondary cell, negative pole or organic dividing plate, also can positive pole, negative pole and organic dividing plate all on film forming.
(3) electrode for secondary battery
As secondary cell, can enumerate: lithium rechargeable battery and nickel-hydrogen secondary cell etc.Wherein, due to lithium rechargeable battery require the raising of fail safe most and perforated membrane to import effect the highest, therefore preferably, therefore, below the situation for lithium rechargeable battery to be described.
Electrode for secondary battery of the present invention contains: collector body, be attached to this collector body and form and electrode active material layer containing electrode active material and binding agent and the above-mentioned secondary cell perforated membrane that is stacked on this electrode active material layer surface.In brief, electrode for secondary battery of the present invention contains the electrode active material layer of electrode active material and binding agent for electrode and the secondary cell perforated membrane that lamination is above-mentioned on the surface of electrode active material layer forms in the surface attachment of collector body.
(electrode active material)
As long as the electrode active material used in electrode for lithium ion secondary battery can reversibly insert the active material of releasing lithium ion by applying electromotive force in the electrolyte, inorganic compound or organic compound all can use.
The electrode active material (positive active material) of lithium ion secondary battery positive electrode is roughly divided into the active material be made up of inorganic compound and the active material be made up of organic compound.As the positive active material be made up of inorganic compound, can enumerate: the composite oxides, transient metal sulfide etc. of transition metal oxide, lithium and transition metal.As above-mentioned transition metal, use Fe, Co, Ni, Mn etc.As the concrete example of the inorganic compound used in positive active material, can enumerate: LiCoO 2, LiNiO 2, LiMnO 2, LiMn 2o 4, LiFePO 4, LiFeVO 4deng lithium-contained composite metal oxide; TiS 2, TiS 3, noncrystalline MoS 2deng transient metal sulfide; Cu 2v 2o 3, noncrystalline V 2o-P 2o 5, MoO 3, V 2o 5, V 6o 13deng transition metal oxide.These compounds can for partly carrying out the compound of element replacement.As the positive active material be made up of organic compound, such as, also can use the electroconductive polymer such as polyacetylene, polyparaphenylene.The ferrous oxide of conductivity deficiency, by there is carbon source material when reduction is fired, also can use as the electrode active material covered with material with carbon element.In addition, these compounds can for partly carrying out the compound that element replaces.
The positive active material of lithium rechargeable battery can be above-mentioned inorganic compound and the mixture of organic compound.The arbitrary constitutive requirements that the particle diameter of positive active material can take into account battery are suitable for selecting, but improve from the viewpoint of the battery behavior such as multiplying power property, cycle characteristics, and 50% volume-cumulative particle diameter is generally 0.1 ~ 50 μm, preferably 1 ~ 20 μm.If 50% volume-cumulative particle diameter is this scope, the secondary cell that charge/discharge capacity is large can be obtained, and processing ease when manufacturing electrode slurry and electrode.50% volume-cumulative particle diameter can by obtaining by determination of laser diffraction particle size distribution.
As the electrode active material (negative electrode active material) of lithium ion secondary battery negative pole, such as, can enumerate: the Electroconductivity of Conducting Polymers etc. such as the carbonaceous materials such as amorphous carbon, graphite, native graphite, carbonaceous mesophase spherules, pitch-based carbon fiber, coalescence benzene.In addition, as negative electrode active material, use the metal such as silicon, tin, zinc, manganese, iron, nickel and their alloy, the oxide of above-mentioned metal or alloy and sulfate.In addition, the lithium alloy such as lithium metal, Li-Al, Li-Bi-Cd, Li-Sn-Cd, lithium transition-metal nitride, silicone etc. can be used.Electrode active material also can to use by mechanically modifying method in surface attachment conduction give the active material of material.Other the constitutive requirements that the particle diameter of negative electrode active material can take into account battery are suitable for selecting, from the viewpoint of the raising of the battery behaviors such as initial efficiency, multiplying power property, cycle characteristics, 50% volume-cumulative particle diameter is generally 1 ~ 50 μm, is preferably 15 ~ 30 μm.
(binding agent for electrode)
In the present invention, electrode active material layer, except electrode active material, (below, is designated as " binding agent for electrode " sometimes containing binding agent.)。By containing binding agent for electrode, the caking property of the electrode active material layer in electrode improves, electrode roll around time etc. operation rises relative to the intensity of the power of this machinery, in addition, electrode active material layer in electrode becomes and not easily departs from, therefore, the danger departing from the short circuit that causes of thing etc. diminishes.
As binding agent for electrode, various resinous principle can be used.Such as can use polyethylene, polytetrafluoroethylene (PTFE), Kynoar (PVDF), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivative, HPAM Degraded Bacteria etc.These may be used singly or in combination of two or more.In addition, also the adhesive being used for perforated membrane of the present invention can be used as binding agent for electrode.
And then, below illustrative soft polymer also can be used as binding agent for electrode.
Acrylic acid series soft polymer can be enumerated: the homopolymers of the acrylic or methacrylic acid derivatives such as butyl polyacrylate, polybutyl methacrylate, polymethylacrylic acid hydroxy methacrylate, polyacrylamide, polyacrylonitrile, n butyl acrylate styrene, butyl acrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile-glycidyl methacrylate copolymer or and can with the copolymer of the monomer of its copolymerization;
The isobutene system soft polymers such as polyisobutene, butyl rubber, isobutylene-styrene copolymer;
The diene series soft polymers such as polybutadiene, polyisoprene, butadiene-styrene random copolymer, isoprene styrene random copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, butadiene-styrene-block copolymer, s-B-S-block copolymer, isoprene styrene-block copolymer, styrene-isoprene-phenylethene-block copolymer;
The siliceous soft polymers such as dimethyl polysiloxane, diphenylpolysiloxane, polysiloxanediol;
The olefin-based soft polymers such as liquid polyethylene, polypropylene, poly-1-butylene, ethene-alpha-olefin copolymer, propylene-alpha-olefin copolymers, ethylene-propylene-diene copolymer (EPDM), ethylene-propylene, Styrene copolymer;
The ethene base system soft polymers such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinylacetate-styrol copolymer;
The epoxy soft polymers such as poly(ethylene oxide), PPOX, epichlorohydrin rubber;
The fluorine-containing soft polymers such as vinylidene fluoride rubber, tetrafluoroethylene-acrylic rubber;
Other the soft polymer etc. such as natural rubber, polypeptide, protein, Polyester thermoplastic elastomer (TPE), vinyl chloride thermoplastic elastomer (TPE), Thermoplastic polyamide elastomer.These soft polymers can have cross-linked structure, in addition, also can import functional group by modification.
The amount of the binding agent for electrode in electrode active material layer is preferably 0.1 ~ 5 mass parts relative to electrode active material 100 mass parts, is more preferably 0.2 ~ 4 mass parts, is particularly preferably 0.5 ~ 3 mass parts.Be above-mentioned scope by the binding agent for electrode amount in electrode active material layer, cell reaction ground inhibit activities material can not be hindered to depart from from electrode.
In order to make electrode, binding agent for electrode is prepared with the form of solution or dispersion liquid.Viscosity is now generally the scope of 1 ~ 300,000mPas, is preferably 50 ~ 10,000mPas.Above-mentioned viscosity be use Brookfield viscometer 25 DEG C, measure under the condition of revolution 60rpm time value.
(arbitrary additive)
In the present invention, electrode active material layer, also can containing the arbitrary additive such as conductive imparting material and reinforcing material except above-mentioned electrode active material and binding agent for electrode.Give material as conduction, can enumerate; The conductive carbon such as acetylene black, Ketjen black, carbon black, graphite, gas-phase growth of carbon fibre, carbon nano-tube.Can enumerate: the fiber of the carbon dusts such as graphite, various metal and paper tinsel etc.As reinforcing material, various inorganic and organically spherical, tabular, bar-shaped or fibrous filler can be used.By using conductivity to give material, electrode active material electrical contact each other can be improved, when for lithium rechargeable battery, discharge-rate characteristic (レ ー ト characteristic can be improved).Conductivity gives the use amount of material and reinforcing material relative to electrode active material 100 mass parts, is generally 0 ~ 20 mass parts, is preferably 1 ~ 10 mass parts.In addition, in electrode active material layer, also isothiazoline based compound and complex compounds can be contained.
Electrode active material layer can make the slurry containing electrode active material, binding agent for electrode and solvent (below, be sometimes referred to as " electrode slurry ".) be attached on collector body and formed.
As solvent, as long as lysis electrodes binding agent or make it be dispersed into granular solvent, preferably carry out the solvent dissolved.If use the solvent of lysis electrodes binding agent, be then adsorbed in the surface of electrode active material and arbitrary additive by binding agent for electrode, the decentralized stabilization of electrode active material etc.
As the solvent for electrode slurry, what can use in water and organic solvent is any.As organic solvent, can enumerate: the annular aliphatic such as pentamethylene, cyclohexane hydro carbons; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; The ketone such as ethyl methyl ketone, cyclohexanone; The ester classes such as ethyl acetate, butyl acetate, gamma-butyrolacton, 6-caprolactone; The nitrile such as acetonitrile, propionitrile; The ethers such as oxolane, ethylene glycol diethyl ether; The alcohols such as methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycol monoethyl ether; The amide-type such as 1-METHYLPYRROLIDONE, DMF.These solvents separately or can mix two or more, from the viewpoint of rate of drying and environmentally suitable choice for use.
The additive of various function can be shown further containing tackifier etc. in electrode slurry.As tackifier, use the polymer dissolving in solvent being used for electrode slurry.Specifically, illustrative tackifier in perforated membrane slurry of the present invention can be used.The use amount of tackifier is preferably 0.5 ~ 1.5 mass parts relative to electrode active material 100 mass parts.If the use amount of tackifier is above-mentioned scope, then the screening characteristics of electrode slurry and good with the adaptation of collector body.
And then, in electrode slurry, except mentioned component, in order to improve stability and the life-span of battery, trifluoro propylene carbonate, vinylene carbonate, catechol carbonate, 1,6-dioxo spiro [4 can be used, 4] nonane-2,7-diketone, 12-crown-4-ether etc.In addition, these can containing using in electrolyte described later.
According to the kind of electrode active material and binding agent for electrode etc., adjust the amount of the solvent in electrode slurry thus form the viscosity being suitable for applying.Specifically, the concentration that preferably adjustment makes electrode active material, binding agent for electrode and conductivity in electrode slurry give the solid constituent that the arbitrary additives such as material amount to is 30 ~ 90 quality %, is more preferably the amount of 40 ~ 80 quality % and uses.
Use mixer by electrode active material, binding agent for electrode, the conductivity of adding as required gives the arbitrary additives such as material and solvent mixes, thus obtain electrode slurry.Above-mentioned each composition also can be supplied in mixer and mix by mixing in the lump.When the constituent using electrode active material, binding agent for electrode, conductivity imparting material and tackifier as electrode slurry, be microgranular owing to conductivity to be given material and tackifier mix in a solvent and make conductivity give dispersion of materials, then, add binding agent for electrode, electrode active material carries out mixing further that the dispersiveness of slurry is improved, therefore preferably.As mixer; ball mill, sand mill, pigment dispersion machine, mixing and kneading machine, ultrasonic dispersing machine, homogenizer, planetary stirring machine, Hobart's mixer etc. can be used; if use ball mill, then conductivity can be suppressed to give the cohesion of material and electrode active material, therefore preferably.
The granularity of electrode slurry is preferably less than 35 μm, more preferably less than 25 μm.If the granularity of slurry is above-mentioned scope, then can obtains conductivity and give the dispersiveness of material the high and electrode of homogeneous.
(collector body)
As long as collector body is for having conductivity and the material with electrochemistry durability is just not particularly limited, from the viewpoint of having thermal endurance, the such as preferred metal material such as iron, copper, aluminium, nickel, stainless steel, titanium, tantalum, gold, platinum.Wherein, as the positive pole use of lithium rechargeable battery, particularly preferably aluminium, as the negative pole use of lithium rechargeable battery, particularly preferably copper.The shape of collector body is not particularly limited, the collector body of the sheet of preferred thickness about 0.001 ~ 0.5mm.Collector body, in order to improve the adhesive strength of electrode active material layer, preferably carries out roughened process to use in advance.As roughened method, can enumerate: mechanical polishing method, electrobrightening method, chemical polishing etc.In mechanical polishing method, use the set sand paper of polishing agent particle, grinding stone, diamond dust, possess the line brush etc. of steel wire etc.In addition, in order to improve adhesive strength and the conductivity of electrode active material layer, intermediate layer can be formed on collector body surface.
As long as the manufacture method of electrode active material layer is for making electrode active material layer be bonded as the method for stratiform at least one side of above-mentioned collector body, preferably two sides.Such as above-mentioned electrode slurry be coated with on the current collector and carry out drying, then more than 120 DEG C, carrying out more than 1 hour heat treated, forming electrode active material layer.Electrode slurry coating method is on the current collector not particularly limited.Such as can enumerate: the methods such as scraper for coating method, infusion process, reverse roll method, directly roller method, intagliotype, extrusion, spread coating.As drying means, can enumerate: utilize the seasoning that the drying of such as warm air, hot blast, low wet wind, vacuumize, utilization (far) infrared ray or electron beam etc. irradiate.
Then, preferably use moulding press or roll squeezer, reduced the voidage of electrode active material layer by pressurized treatments.The preferred scope of voidage is 5 ~ 15%, is more preferably 7 ~ 13%.If voidage is too high, then charge efficiency and discharging efficiency are deteriorated.When voidage is too low, produces and be difficult to obtain high volume capacity or electrode active material layer easily peels off and easily produces the such problem of unfavorable condition.And then, when using the polymer of curability, be preferably cured.
For the thickness of electrode active material layer, positive pole, negative pole are all generally 5 ~ 300 μm, are preferably 10 ~ 250 μm.
Electrode for secondary battery of the present invention by bonding promising stratiform electrode active material layer collector body electrode active material layer on the surface lamination secondary cell perforated membrane of the present invention manufacture.
Laminating method is not particularly limited, and can enumerate: the method for (I) that illustrate in the manufacture method of above-mentioned perforated membrane ~ (III).
(4) secondary battery separator
The above-mentioned secondary cell perforated membrane that secondary battery separator of the present invention contains institute's lamination on organic dividing plate, this organic dividing plate forms.In brief, secondary battery separator of the present invention forms at the secondary cell perforated membrane that organic dividing plate superimposed layer is above-mentioned.
(organic dividing plate)
As organic dividing plate of lithium rechargeable battery, use the known dividing plate such as the vistanex such as polyethylene, polypropylene or the dividing plate containing aromatic polyamide resin.
As for organic dividing plate of the present invention, use does not have electronic conductivity and has ionic conductivity, high and the multiple aperture plasma membrane that aperture is fine of the patience of organic solvent, can enumerate by such as polyolefin (polyethylene, polypropylene, polybutene, polyvinyl chloride), and the resin such as these mixture or copolymer forms micro-porous film, by PETG, polycyclic alkene, polyether sulfone, polyamide, polyimides, polyimide amide, Nomex, polycyclic alkene, nylon, the fibrage of the micro-porous film that the resin such as polytetrafluoroethylene is formed or polyolefin, or its nonwoven fabrics, the aggregate etc. of insulating properties material grains.Wherein, excellent from the screening characteristics of perforated membrane slurry of the present invention, can thinning dividing plate entirety thickness, improve the active material ratio in battery and the aspect improving the capacity of unit volume is considered, the micro-porous film be preferably made up of the resin of polyolefin.
The thickness of organic dividing plate is generally 0.5 ~ 40 μm, is preferably 1 ~ 30 μm, more preferably 1 ~ 20 μm.If this scope, then the resistance decreasing that the organic dividing plate in battery brings.In addition, by good for the operability of perforated membrane slurry coating of the present invention when organic dividing plate.
In the present invention, as the resin of polyolefin of material being used as organic dividing plate, can enumerate: the homopolymers of polyethylene, polypropylene etc., copolymer and their mixture.As polyethylene, can enumerate low-density, Midst density, highdensity polyethylene, from the viewpoint of puncture strength and mechanical strength, preferred highdensity polyethylene.In addition, these polyethylene are considered from the object of giving flexibility, also can mix two or more.Also be not particularly limited for these poly polymerization catalysts, can enumerate: Z-N series catalysts, Philips series catalysts and metallocene series catalysts etc.From the viewpoint of having both mechanical strength and high-permeability, poly viscosity average molecular weigh preferably 100,000 ~ 1,200 ten thousand, is more preferably 200,000 ~ 3,000,000.As polypropylene, can enumerate: homopolymers, random copolymer, block copolymer, can be mixed one or two or more kinds and use.In addition, polymerization catalyst is also not particularly limited, and can enumerate: Z-N series catalysts and metallocene series catalysts etc.In addition, stereospecificity is also not particularly limited, and can use isotaxy, syndiotaxy and atactic, but from the viewpoint of cheapness, preferably use isotactic polypropylene.And then, in the scope not damaging effect of the present invention, in polyolefin, also can add the polyolefin beyond polyethylene or polypropylene and the additive such as antioxidant, nucleator in right amount.
As the method for organic dividing plate of making polyolefin, public method can be used, such as can select from following method: polypropylene, polyethylene are melt extruded after making film, it is made to anneal at low temperatures, crystallized domains is grown, stretch in this condition, non-crystalline areas is stretched, form the dry method of micro-porous film thus; After hydrocarbon solvent and other low molecule material and polypropylene, polyethylene mixing, form film, then, collect for solvent in amorphous phase and low molecule and start to be formed the film of island phase, hold volatile solvent by using other and remove this solvent, low molecule, form the wet method etc. of micro-porous film thus.Wherein, from the viewpoint of for falling low-resistance object, easily obtaining larger space, preferred dry method.
For the object of control intensity and hardness, percent thermal shrinkage, also arbitrary filler and compound can be contained for organic dividing plate of the present invention.In addition, when lamination perforated membrane of the present invention, for make the adaptation of organic dividing plate and perforated membrane improve or reduce relative to electrolyte surface tension and make the object that the impregnation of liquid improves, also can carry out coating treatment with low molecular compound or macromolecular compound in advance or carry out the plasma treatment such as electromagnetic wire process, corona discharge-plasma gas such as ultraviolet.
Particularly high and easily obtain with the adaptation of above-mentioned perforated membrane from the viewpoint of the impregnation of electrolyte, preferably carry out coating treatment with the macromolecular compound containing carboxylic acid group, hydroxyl and sulfonic group isopolarity group.
Secondary battery separator of the present invention is by manufacturing at above-mentioned organic dividing plate superimposed layer secondary cell perforated membrane of the present invention.
Laminating method is not particularly limited, and can enumerate: the method that (I) ~ (III) is described in the manufacture method of above-mentioned perforated membrane.
(5) secondary cell
Secondary cell of the present invention contains positive pole, negative pole, organic dividing plate and electrolyte, and the perforated membrane above-mentioned at any superimposed layer of positive pole, negative pole and organic dividing plate forms.
(electrolyte)
As electrolyte, use and dissolved the organic electrolyte of supporting electrolyte in organic solvent.As supporting electrolyte, use lithium salts.As lithium salts, be not particularly limited, can enumerate: LiPF 6, LiAsF 6, LiBF 4, LiSbF 6, LiAlCl 4, LiClO 4, CF 3sO 3li, C 4f 9sO 3li, CF 3cOOLi, (CF 3cO) 2nLi, (CF 3sO 2) 2nLi, (C 2f 5sO 2) NLi etc.Wherein, preferably soluble in solvent and the LiPF of the higher degree of dissociation of display 6, LiClO 4, CF 3sO 3li.These also can combinationally use more than two kinds.Because the supporting electrolyte lithium ion conduction degree more using degree of dissociation high is higher, therefore, lithium ion conduction degree can be regulated according to the kind of supporting electrolyte.
As the organic solvent for electrolyte, as long as the solvent that can dissolve supporting electrolyte is just not particularly limited, the carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), methyl ethyl carbonate (MEC) preferably can be used; The ester such as gamma-butyrolacton, methyl formate class; The ethers such as 1,2-dimethoxy-ethane, oxolane; The sulfur-containing compound such as sulfolane, dimethyl sulfoxide (DMSO) class.In addition, the mixed liquor of these solvents can also be used.Wherein, due to the voltage belt field width that carbonates dielectric constant is high, stable, therefore preferably.Because the viscosity of the solvent used is lower, lithium ion conduction degree becomes higher, therefore, can regulate lithium ion conduction degree according to the kind of solvent.
The concentration of the supporting electrolyte in electrolyte is generally 1 ~ 30 quality %, is preferably 5 ~ 20 quality %.In addition, according to the kind of supporting electrolyte, usually use with the concentration of 0.5 ~ 2.5 mole/L.The concentration of supporting electrolyte too low or too high all exist ionic conductance reduce tendency.Because the swellbility of the concentration more low polymer particle of electrolyte used becomes larger, therefore, can according to the concentration adjustment lithium ion conduction degree of electrolyte.
As the concrete manufacture method of secondary cell, can enumerate: carry out superimposed by positive pole and negative pole via organic dividing plate, it is curling according to cell shapes, bending etc. puts into battery case, inject electrolyte and the method for sealing to battery case.Perforated membrane of the present invention be stacked in positive pole, negative pole and organic dividing plate any on.Described in method perforated membrane of the present invention being stacked on the method described above (I) or (II) of positive pole, negative pole and organic dividing plate.In addition, described in the method for (III) described above, also only perforated membrane can be stacked on positive pole, negative pole or organic dividing plate independently.Also can put into the overcurrent such as expansion alloy, fuse, PTC element as required to prevent from element, lead plate etc. to prevent the pressure increase of inside battery, cross discharge and recharge.The shape of battery can be any shapes such as Coin shape, coin shape, flap-type, cylinder type, square, platypelloid type.
In secondary cell of the present invention, preferably perforated membrane of the present invention is stacked on the electrode active material layer surface of negative or positive electrode.By perforated membrane of the present invention is stacked on electrode active material layer surface, even if the contraction that organic dividing plate causes thermal conductance to cause, also can not cause the short circuit between positive pole, negative pole, guarantee higher fail safe.In addition, by perforated membrane of the present invention is stacked on electrode active material layer surface, even without organic dividing plate, perforated membrane also can play the function as dividing plate, can with low-cost production's secondary cell.In addition, even if when using organic dividing plate, the hole that baffle surface is formed also can not be filled up, can show higher multiplying power property.
Embodiment
Below, the present invention will be described to enumerate embodiment, but the present invention is not limited thereto.Be explained, the part in the present embodiment and % unless otherwise specified, are then quality criteria.In embodiment and comparative example, various physical property is evaluated as follows.
Heat resisting temperature (T10 value) > of the non-conductive particle of <
Under nitrogen atmosphere, heat from 30 DEG C with thermobalance with programming rate 10 DEG C/min, the loss of weight ratio obtaining non-conductive particle reaches the temperature [DEG C] of 10 quality %, as heat resisting temperature.
The average grain diameter > of the non-conductive particle of <
100 non-conductive particles are at random selected from the photo taken with the multiplying power of 25000 times with electron microscope, the longest edge of its particle picture is set to a, will most minor face when being set to b, (a+b)/2 are set to particle diameter, calculate average grain diameter [μm] by 100 mean values.
The average circularity > of the non-conductive particle of <
From the photo taken with the multiplying power of 25000 times with electron microscope, at random select 100 non-conductive particles, the girth of the circle with the projected area identical with its particle image is set to L 0, when the girth of particle image is set to L, by L 0/ L is set to circularity, calculates average circularity by 100 mean values.
The domain size distribution > of the non-conductive particle of <
The volume average particle size obtained after (LS230) carry out particle size determination, is set to V, number average bead diameter is set to N, obtain with following formula by the laser diffraction refraction particle size distribution device of domain size distribution Beckman Co., Ltd. of non-conductive particle.
Domain size distribution=V/N
The uniformity > of < perforated membrane
Secondary cell perforated membrane (organic dividing plate of band perforated membrane) or electrode for secondary battery (electrode of band perforated membrane) are cut into width 10cm × length 1.5m, the thickness gauge of Co., Ltd. Nikon (MH-15M) is used by the thickness of the secondary cell perforated membrane be cut into or electrode for secondary battery to measure in 5cm, 20 60 at Width 3 points × length direction, calculate the inequality [%] of thickness by the standard deviation of thickness and mean value based on following formula, evaluate with following benchmark.
[mathematical expression 1]
The standard deviation of thickness &sigma; = n&Sigma; x 2 - ( &Sigma;x ) 2 n 2
Inequality=σ/x × 100 (%) of thickness
At this, x represents the mean value of thickness, and n represents mensuration number.
(metewand)
A: lower than 2%
More than B:2% ~ lower than 3%
More than C:3% ~ lower than 10%
More than D:10%
The reliability test > of < secondary battery separator (organic dividing plate of band perforated membrane)
Secondary battery separator (organic dividing plate of band perforated membrane) is punching into the circle of diameter 19mm, in nonionic surfactant (KAO. Corp. SA's system; Emulgen210P) dipping in 3 % by weight methanol solutions is also air-dry.Impregnation electrolyte in the secondary battery separator of this circle, is held on the SUS plate (diameter 15.5mm) of a pair circle, is overlapped into (SUS plate)/such the structure of (circular secondary battery separator)/(SUS plate).At this, electrolyte is used in mixed solvent ethylene carbonate (EC) and diethyl carbonate (DEC) mixed with EC:DEC=1:2 (volumetric ratios at 20 DEG C) and dissolves LiPF with the concentration of 1 mol/L 6solution.Enclosed 2032 type coin batteries.From this coin battery, get lead-in wire, put into the baking box of additional heat galvanic couple.Apply the alternating current of the frequency of amplitude 10mV, 1kHz while be warming up to 200 DEG C with programming rate 1.6 DEG C/min, measure the cell resistance of this process, confirm the situation occurred of short circuit thus.In this test, while temperature rises, due to cut-out, resistance value rises, and is at least 1000 Ω/cm 2above.Then, 10 Ω/cm are reduced to rapidly 2following situation is set to short circuit and occurs.In addition, carry out this test 20 times, evaluate with following benchmark.
(metewand)
A: short circuit occurs several 0
B: short circuit occurs several 1
C: short circuit occurs several 2 ~ 3
D: short circuit occurs several more than 4
The reliability test > of < electrode for secondary battery (electrode of band perforated membrane)
Organic dividing plate (the polypropylene dividing plate of individual layer, the porosity 55%, thickness 25 μm) is punching into the circle of diameter 19mm, is immersed in nonionic surfactant (KAO. Corp. SA's system; Emulgen210P) air-dry in 3 % by weight methanol solutions.On the other hand, the electrode for secondary battery (electrode of band perforated membrane) of determination object is punching into the circle of diameter 19mm.Make their impregnation electrolyte and they are overlapping, be held on the SUS plate (diameter 15.5mm) of a pair circle, be overlapped into (SUS plate)/such the structure of (circular organic dividing plate)/(circular electrode for secondary battery)/(SUS plate).Arranging circular electrode for secondary battery makes the face of its perforated membrane side be organic bulkhead sides.At this, electrolyte is used in mixed solvent ethylene carbonate (EC) and diethyl carbonate (DEC) mixed with EC:DEC=1:2 (volumetric ratios at 20 DEG C) and dissolves LiPF with the concentration of 1 mol/L 6solution.Enclosed 2032 type coin batteries.From coin battery, get lead-in wire, put into the baking box of additional heat galvanic couple.Apply the alternating current of the frequency of amplitude 10mV, 1kHz while be warming up to 200 DEG C with programming rate 1.6 DEG C/min, measure the cell resistance of this process, confirm the situation occurred of short circuit thus.In this test, while temperature rises, due to cut-out, resistance value rises, and is at least 1000 Ω/cm 2above.Then 10 Ω/cm are reduced to rapidly 2following situation is set to short circuit.In addition, carry out this test 20 times, evaluate with following benchmark.
(metewand)
A: short circuit occurs several 0
B: short circuit occurs several 1 ~ 2
C: short circuit occurs several more than 3
The cycle characteristics > of < secondary cell
By at 20 DEG C with the constant current charge of 0.2C to 4.3V, using the constant-current discharge of 0.2C to the operation of 3.0V as 1 circulation, repetition discharge and recharge is carried out to the secondary cell obtained (Coin-shaped battery).Calculate the ratio of the discharge capacity in the 100th circulation relative to the discharge capacity in the 2nd circulation as charge/discharge cycle characteristics using percentage, judge with following benchmark.This value is larger, represents that the capacity that repetition discharge and recharge causes reduces fewer.
(metewand)
More than A:97%
More than B:95% and lower than 97%
More than C:90% and lower than 95%
More than D:85% and lower than 90%
E: lower than 85%
The powder falling > of < electrode for secondary battery (electrode of band perforated membrane)
Electrode for secondary battery (electrode of band perforated membrane) is cut into 5cm square, puts into the vial of 500ml, vibrate 3 hours with 300rpm with oscillator.The quality of powder falling is considered as a, the quality of electrode for secondary battery before vibration is considered as b, the quality of the electrode before laminated porous film be considered as c, by non-laminated porous film only electrode vibration time the quality of powder falling be considered as d, calculate the ratio X [quality %] of powder falling by following formula, evaluate with following benchmark.
X=(a-d)/(b-c-a) × 100 [quality %]
(metewand)
A: lower than 2 quality %
More than B:2 quality % and lower than 5 quality %
More than C:5 quality %
The powder falling > of < secondary battery separator (organic dividing plate of band perforated membrane)
Secondary battery separator (organic dividing plate of band perforated membrane) is cut into 5cm square, puts into the vial of 500ml, vibrate 3 hours with 300rpm with oscillator.The ratio X [quality %] quality of the secondary battery separator before vibration being considered as a, the quality of the secondary battery separator after vibration being considered as b, calculating powder falling with following formula, evaluates with following benchmark.
X=(a-b)/a × 100 [quality %]
(metewand)
A: lower than 1 quality %
More than B:1 quality % and lower than 3 quality %
More than C:3 quality % and lower than 5 quality %
More than D:5 quality % and lower than 10 quality %
More than E:10 quality %
The mensuration > containing ratio of the sulfonic group in < polymer beads and epoxy radicals
If the addition [g] with sulfonic monomer added when the polymerization of acrylic polymer particles A is considered as a, molecular weight is considered as b, molecular weight suitable for sulfonyloxy portion is considered as c (81.07), monomer total amount is considered as d, then in acrylic polymer particles A, the sulfonic of (relative to monomer total amount) is calculated by the mode of following formula containing ratio [quality %].
Sulfonic containing ratio (A) in acrylic polymer particles A
=(a/b) × c/d × 100 [quality %]
Equally, if the addition [g] with the monomer of epoxy radicals added when the polymerization of acrylic polymer particles B is considered as e, molecular weight is considered as f, molecular weight suitable for epoxy radicals part is considered as g (43.05), monomer total amount is considered as h, then in acrylic polymer particles B, the ratio [quality %] that contains of the epoxy radicals of (relative to monomer total amount) is calculated by the mode of following formula.
Epoxy radicals in acrylic polymer particles B containing ratio (B)
=(e/f) × g/h × 100 [quality %]
Sulfonic group in < adhesive is relative to the mensuration > of the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals
The solid constituent amount [g] of the acrylic polymer particles A added when slurry makes is considered as C, the solid constituent amount [g] of the acrylic polymer particles B added when slurry makes is considered as D.And then, use the sulfonic group in polymer beads and epoxy radicals containing sulfonic containing ratio (B) containing in ratio (A) and acrylic polymer particles B of sulfonic in the acrylic polymer particles A obtained in the mensuration of ratio, calculated the weight ratio of sulfonic group/epoxy radicals by following manner.
Sulfonic group/epoxy radicals=(A × C)/(B × D) [weight ratio]
(embodiment 1)
The manufacture > of < (1) seeding polymerization composition granule A
In the reactor with mixer, put into styrene 100 parts, neopelex 1.0 parts, ion exchange water 100 parts and potassium peroxydisulfate 0.5 part, be polymerized 8 hours at 80 DEG C.Thus, the aqueous dispersion of the seeding polymerization composition granule A of average grain diameter 60nm is obtained.
The manufacture > of < (2) seeding polymerization composition granule B
The aqueous dispersion putting into the seeding polymerization composition granule A that operation (1) obtains in the reactor with mixer with solid constituent benchmark (i.e. the weight basis of seeding polymerization composition granule A) count 2 parts, neopelex 0.2 part, potassium peroxydisulfate 0.5 part and ion exchange water 100 parts, mix, obtain mixture, be warming up to 80 DEG C.On the other hand, in another container, benzene mixed ethene 97 parts, methacrylic acid 3 parts, tertiary lauryl mercaptan 4 parts, neopelex 0.5 part and ion exchange water 100 parts, prepare the dispersion of monomer mixture.The dispersion of this monomer mixture being added into continuously in said mixture through 4 hours makes it be polymerized.The temperature of the reaction system in the continuous adding procedure of the dispersion of monomer mixture remains 80 DEG C, reacts.After continuous print interpolation terminates, at 90 DEG C, continue reaction 3 hours further.
Thus, the aqueous dispersion of the seeding polymerization composition granule B of average grain diameter 200nm is obtained.
The manufacture > of < (3) non-conductive particle
Then, the aqueous dispersion of the seeding polymerization composition granule B that operation (2) obtains is put in solid constituent benchmark (i.e. seeding polymerization composition granule B weight basis) 10 parts in the reactor with mixer, monomer mixture (the mixture of divinylbenzene and vinyl xylene, ethyl vinyl benzene, monomer mixing ratio: divinylbenzene/vinyl xylene, ethyl vinyl benzene=60/40, chemical company of Nippon Steel system, goods name: DVB-570) 90 parts, neopelex 1 part, as peroxidating (2 ethyl hexanoic acid) tert-butyl ester (the You Inc. of polymerization initiator, trade name: Perbutyl O) 5 parts and ion exchange water 200 parts, stir 12 hours at 35 DEG C, seeding polymerization composition granule B is made to absorb monomer mixture and polymerization initiator completely thus.Then, it is polymerized 4 hours at 90 DEG C.Then, import steam and remove unreacted monomer.
Thus, the aqueous dispersion of the non-conductive particle of average grain diameter 0.4 μm is obtained.
From seeding polymerization composition granule be formed to obtain non-conductive particle till the heat resisting temperature (T10 value) of the composition of monomer (styrene, methacrylic acid, divinylbenzene and vinyl xylene, ethyl vinyl benzene) that uses and non-conductive particle, average circularity and domain size distribution as shown in table 1.
The making > of < (4) acrylic polymer particles A
Ion exchange water 300 parts, n-butyl acrylate 81.1 parts, acrylonitrile 14.9 parts, 2-acrylamide-2-methyl propane sulfonic 4.0 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles A of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles A have sulfonic monomeric unit containing ratio be 4.0%, sulfonic containing ratio be 1.56%, acrylonitrile monomer unit containing ratio be 14.9%, (methyl) acrylate monomeric units be 81.1% containing ratio.
The making > of < (5) acrylic polymer particles B
Ion exchange water 300 parts, n-butyl acrylate 81.9 parts, acrylonitrile 15.1 parts, glycidyl methacrylate 3.0 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles B containing average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles B have the monomeric unit of epoxy radicals containing ratio be 3.0%, epoxy radicals containing ratio be 0.91%, acrylonitrile monomer unit containing ratio be 15.1%, (methyl) acrylate monomeric units containing ratio be 81.9%.
The manufacture > of < (6) perforated membrane slurry
As tackifier, use degree of etherification falling to be 0.8 ~ 1.0,1% solution viscosity be the carboxymethyl cellulose (Daicel chemical industry Co., Ltd. Daicel1220) of 10 ~ 20mPas, prepared 1% aqueous solution.
The aqueous dispersions of acrylic polymer particles B obtained in the aqueous dispersions of the acrylic polymer particles A obtained in the aqueous dispersion of the non-conductive particle obtained in operation (3), operation (4), operation (5) and 1% aqueous solution of carboxy methyl cellulose are mixed than for the mode of 83.1:6.15:6.15:4.6 with solids by weight in water, add water further as solvent, use ball mill to make it disperse to obtain perforated membrane slurry.In addition, the content of the raw material (total amount of solid constituent) beyond the water in perforated membrane slurry is 50 quality %.
In addition, the acrylic polymer particles A in perforated membrane slurry relative to the weight ratio (acrylic polymer particles A/ acrylic polymer particles B) of acrylic polymer particles B be 1, sulfonic group in adhesive is 1.7 relative to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The manufacture > of < (7) positive pole
The mode being 3 parts using solid constituent conversion gauge in as the LiMn2O4 with spinel structure 95 parts of positive active material adds the PVDF (Kynoar, Wu Yu chemistry Inc., trade name: KF-1100) as binding agent for electrode, and then, add acetylene black 2 parts and 1-METHYLPYRROLIDONE 20 parts, they are mixed with planetary stirring machine, obtains the positive pole electrod composition (positive pole slurry) of pulp-like.This positive pole slurry is coated in the one side of the aluminium foil of thickness 18 μm, at 120 DEG C after dry 3 hours, carry out roll-in and obtain the positive pole with positive electrode active material layer that gross thickness is 100 μm.
The manufacture > of < (8) negative pole
Using particle diameter 20 μm, specific area 4.2m as negative electrode active material 298 parts, the graphite of/g and solid constituent conversion amount are the SBR as binding agent for electrode (styrene butadiene rubbers, glass transition temperature :-10 DEG C) mixing of 1 part, mix carboxy methyl cellulose 1.0 parts further in the mixture, add water further as solvent, they are mixed with planetary stirring machine, has prepared the negative pole electrod composition (negative pole slurry) of pulp-like.This negative pole slurry is coated in the one side of the Copper Foil of thickness 18 μm, at 120 DEG C after dry 3 hours, carry out roll-in system, obtain the negative pole with negative electrode active material layer that gross thickness is 60 μm.
The manufacture > of < (9) secondary battery separator (organic dividing plate of band perforated membrane)
Prepare the polypropylene dividing plate (porosity 55%, thickness 25 μm) of the individual layer manufactured by dry process as organic dividing plate.The mode that the face of the side of this organic dividing plate is 5 μm with dried thickness uses the perforated membrane slurry obtained in bar (wire bar) painting process (6) to obtain pulp layer, by pulp layer at 50 DEG C dry 10 minutes, form perforated membrane.Next, the face of the opposite side of organic dividing plate forms perforated membrane similarly, obtain organic dividing plate of the band perforated membrane on two sides with perforated membrane.
< (10) has the manufacture > of the secondary cell of secondary battery separator (organic dividing plate of band perforated membrane)
The positive pole obtained in operation (7) is cut into the circle of diameter 13mm, obtains circular positive pole.The negative pole obtained in operation (8) is cut into the circle of diameter 14mm, obtains circular negative pole.In addition, organic dividing plate of the band perforated membrane obtained in operation (9) is cut into the circle of diameter 18mm, obtains organic dividing plate of circular band perforated membrane.
Be provided with polypropylene liner stainless steel Coin shape exterior package container inner bottom surface on load circular positive pole, load organic dividing plate of circular band perforated membrane thereon, load circular negative pole further thereon, they are accommodated in container.The circular positive pole of mounting make the bottom surface side of face towards exterior package container of its aluminium foil side, positive electrode active material layer side face towards upside.The circular negative pole of mounting makes the face of its negative electrode active material layer side towards the face of organic bulkhead sides of the band perforated membrane of this circle, Copper Foil side towards upside.By container vacuumize 24 hours at 105 DEG C.
Inject electrolyte in a reservoir thus not residual air, fixing via the stainless lid of polypropylene liner thickness 0.2mm on exterior package container upper cover, battery can is sealed, has manufactured diameter 20mm, lithium rechargeable battery (coin battery CR2032) that thickness is about 3.2mm.As electrolyte, be used in the mixed solvent that ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed with EC:DEC=1:2 (volumetric ratios at 20 DEG C) and dissolve LiPF with the concentration of 1 mol/L 6solution.
< (11) evaluates >
The uniformity of the perforated membrane of organic dividing plate of the band perforated membrane obtained and reliability, powder falling and the cycle characteristics of secondary cell that obtains are evaluated.Show the result in table 1.
(embodiment 2)
In the one side of the negative electrode active material layer side of the negative pole obtained in the operation (8) of embodiment 1 coating Examples 1 operation (6) in the perforated membrane slurry that obtains obtain pulp layer and make it cover negative electrode active material layer completely and dried perforated membrane thickness is 5 μm.By pulp layer at 50 DEG C dry 10 minutes, form perforated membrane, obtain the negative pole of band perforated membrane.The negative pole of the band perforated membrane obtained has the such Rotating fields of (perforated membrane)/(negative electrode active material layer)/(Copper Foil).The uniformity of the perforated membrane of the negative pole of the band perforated membrane obtained and reliability, powder falling are evaluated.Show the result in table 1.
Replace the organic dividing plate of band perforated membrane obtained in the operation (9) of embodiment 1, employ organic dividing plate (the polypropylene dividing plate of individual layer, the porosity 55%, thickness 25 μm, identical with the dividing plate being used as organic dividing plate in the operation (9) of embodiment 1).
In addition, replace the negative pole obtained in the operation (8) of embodiment 1, use the negative pole of above-mentioned band perforated membrane, in addition, carry out operation similarly to Example 1, obtain secondary cell and evaluate.Show the result in table 1.In addition, when the negative pole of the band perforated membrane of circle is positioned in exterior package container, with the one side of its perforated membrane side towards organic dividing plate side of circle, the face of Copper Foil side loads towards the mode of upside.
(embodiment 3)
Replace the acrylic polymer particles A obtained in the operation (4) of embodiment 1, use following acrylic polymer particles A.In addition, replace the acrylic polymer particles B obtained in the operation (5) of embodiment 1, use following acrylic polymer particles B.Use this acrylic polymer particles A and this acrylic polymer particles B to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.In addition, the acrylic polymer particles A in perforated membrane slurry relative to the weight ratio (acrylic polymer particles A/ acrylic polymer particles B) of acrylic polymer particles B be 1, sulfonic group in adhesive is 1.7 relative to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making > of < acrylic polymer particles A
Ion exchange water 300 parts, n-butyl acrylate 89.0 parts, acrylonitrile 7.0 parts, 2-acrylamide-2-methyl propane sulfonic 4.0 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles A1 of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles A have sulfonic monomeric unit containing ratio be 4.0%, sulfonic containing ratio be 1.56%, acrylonitrile monomer unit containing ratio be 7%, (methyl) acrylate monomeric units be 89% containing ratio.
The making > of < acrylic polymer particles B
Ion exchange water 300 parts, n-butyl acrylate 90.0 parts, acrylonitrile 7.0 parts, glycidyl methacrylate 3.0 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles B of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles B have the monomeric unit of epoxy radicals containing ratio be 3.0%, epoxy radicals containing ratio be 0.91%, acrylonitrile monomer unit containing ratio be 7%, (methyl) acrylate monomeric units containing ratio be 90.0%.
(embodiment 4)
Replace the acrylic polymer particles A obtained in the operation (4) of embodiment 1, use following acrylic polymer particles A.In addition, replace the acrylic polymer particles B obtained in the operation (5) of embodiment 1, use following acrylic polymer particles B.Use this acrylic polymer particles A and this acrylic polymer particles B to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
In addition, the acrylic polymer particles A in perforated membrane slurry relative to the weight ratio (acrylic polymer particles A/ acrylic polymer particles B) of acrylic polymer particles B be 1, sulfonic group in adhesive is 1.7 relative to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making > of < acrylic polymer particles A
Ion exchange water 300 parts, n-butyl acrylate 66.1 parts, acrylonitrile 29.9 parts, 2-acrylamide-2-methyl propane sulfonic 4.0 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles A of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles A have sulfonic monomeric unit containing ratio be 4.0%, sulfonic containing ratio be 1.56%, acrylonitrile monomer unit containing ratio be 29.9%, (methyl) acrylate monomeric units be 66.1% containing ratio.
The making > of < acrylic polymer particles B
Ion exchange water 300 parts, n-butyl acrylate 66.8 parts, acrylonitrile 30.2 parts, glycidyl methacrylate 3.0 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles B of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles B have the monomeric unit of epoxy radicals containing ratio be 3.0%, epoxy radicals containing ratio be 0.91%, acrylonitrile monomer unit containing ratio be 30.2%, (methyl) acrylate monomeric units containing ratio be 66.8%.
(embodiment 5)
Replace the non-conductive particle obtained in operation (1) ~ (3) of embodiment 1, following non-conductive particle is used to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
The manufacture > of the non-conductive particle of <
The operation (1) of embodiment 1 is put in the reactor with mixer, (2) aqueous dispersion of the seeding polymerization composition granule B obtained in counts 10 parts with solid constituent benchmark (i.e. seeding polymerization composition granule B weight basis), mixture (the monomer mixing ratio: divinylbenzene/vinyl xylene, ethyl vinyl benzene=60/40 of divinylbenzene and vinyl xylene, ethyl vinyl benzene, chemical company of Nippon Steel system, goods name: DVB-570) 33 parts, vinyl xylene, ethyl vinyl benzene 57 parts, neopelex 1 part, as peroxidating (2 ethyl hexanoic acid) tert-butyl ester (the You society system of polymerization initiator, trade name: Perbutyl O) 5 parts and ion exchange water 200 parts, stir 12 hours at 35 DEG C, seeding polymerization composition granule B is made to absorb monomer mixture and polymerization initiator completely thus.Then, it is polymerized 4 hours at 90 DEG C.Then, import steam and remove unreacted monomer.
Thus, the aqueous dispersion of the non-conductive particle of average grain diameter 0.4 μm is obtained.
From seeding polymerization composition granule be formed to obtain non-conductive particle till the heat resisting temperature (T10 value) of the composition of monomer (styrene, methacrylic acid, divinylbenzene and vinyl xylene, ethyl vinyl benzene) that uses and non-conductive particle, average circularity and domain size distribution as shown in table 1.
(embodiment 6)
Replace the non-conductive particle obtained in operation (1) ~ (3) of embodiment 1, following non-conductive particle is used to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
The manufacture > of < seeding polymerization composition granule A
In the reactor with mixer, put into styrene 95 parts, divinylbenzene 5 parts, neopelex 1.0 parts, ion exchange water 100 parts and potassium peroxydisulfate 0.5 part, be polymerized 8 hours at 80 DEG C.Thus, the aqueous dispersion of the seeding polymerization composition granule A of average grain diameter 60nm is obtained.
The manufacture > of the non-conductive particle of <
The aqueous dispersion of above-mentioned seeding polymerization composition granule A is used in the reactor with mixer, in addition, operate in the same manner as the operation (2) of embodiment 1, (3), obtain the aqueous dispersion that average circularity is the non-conductive particle of 0.91.From seeding polymerization composition granule be formed to obtain non-conductive particle till the heat resisting temperature (T10 value) of the composition of monomer (styrene, methacrylic acid, divinylbenzene and vinyl xylene, ethyl vinyl benzene) that uses and non-conductive particle, average grain diameter and domain size distribution as shown in table 1.
(embodiment 7)
Replace the acrylic polymer particles A obtained in the operation (4) of embodiment 1, use following acrylic polymer particles A.In addition, replace the acrylic polymer particles B obtained in the operation (5) of embodiment 1, use following acrylic polymer particles B.Use this acrylic polymer particles A and this acrylic polymer particles B to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
In addition, the acrylic polymer particles A in perforated membrane slurry relative to the weight ratio (acrylic polymer particles A/ acrylic polymer particles B) of acrylic polymer particles B be 1, sulfonic group in adhesive is 3.4 relative to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making > of < acrylic polymer particles A
Ion exchange water 300 parts, n-butyl acrylate 80.2 parts, acrylonitrile 14.8 parts, 2-acrylamide-2-methyl propane sulfonic 5.0 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles A of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles A have sulfonic monomeric unit containing ratio be 5.0%, sulfonic containing ratio be 1.95%, acrylonitrile monomer unit containing ratio be 14.8%, (methyl) acrylate monomeric units be 80.2% containing ratio.
The making > of < acrylic polymer particles B
Ion exchange water 300 parts, n-butyl acrylate 82.9 parts, acrylonitrile 15.2 parts, glycidyl methacrylate 1.9 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles B of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles B have the monomeric unit of epoxy radicals containing ratio be 1.9%, epoxy radicals containing ratio be 0.58%, acrylonitrile monomer unit containing ratio be 15.2%, (methyl) acrylate monomeric units containing ratio be 82.9%.
(embodiment 8)
Replace the acrylic polymer particles A obtained in the operation (4) of embodiment 1, use following acrylic polymer particles A.In addition, replace the acrylic polymer particles B obtained in the operation (5) of embodiment 1, use following acrylic polymer particles B.Use this acrylic polymer particles A and this acrylic polymer particles B to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
In addition, the acrylic polymer particles A in perforated membrane slurry relative to the weight ratio (acrylic polymer particles A/ acrylic polymer particles B) of acrylic polymer particles B be 1, sulfonic group in adhesive is 0.6 relative to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making > of < acrylic polymer particles A
Ion exchange water 300 parts, n-butyl acrylate 82.6 parts, acrylonitrile 15.2 parts, 2-acrylamide-2-methyl propane sulfonic 2.2 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles A of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles A have sulfonic monomeric unit containing ratio be 2.2%, sulfonic containing ratio be 0.86%, acrylonitrile monomer unit containing ratio be 15.2%, (methyl) acrylate monomeric units be 82.6% containing ratio.
The making > of < acrylic polymer particles B
Ion exchange water 300 parts, n-butyl acrylate 80.5 parts, acrylonitrile 14.8 parts, glycidyl methacrylate 4.7 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles B of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles B have the monomeric unit of epoxy radicals containing ratio be 4.7%, epoxy radicals containing ratio be 1.42%, acrylonitrile monomer unit containing ratio be 14.8%, (methyl) acrylate monomeric units containing ratio be 80.5%.
(embodiment 9)
Replace the acrylic polymer particles A obtained in the operation (4) of embodiment 1, use following acrylic polymer particles A.In addition, replace the acrylic polymer particles B obtained in the operation (5) of embodiment 1, use following acrylic polymer particles B.Use this acrylic polymer particles A and this acrylic polymer particles B to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
In addition, the acrylic polymer particles A in perforated membrane slurry relative to the weight ratio (acrylic polymer particles A/ acrylic polymer particles B) of acrylic polymer particles B be 1, sulfonic group in adhesive is 2.8 relative to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making > of < acrylic polymer particles A
Ion exchange water 300 parts, n-butyl acrylate 76.2 parts, acrylonitrile 14.0 parts, 2-acrylamide-2-methyl propane sulfonic 9.8 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles A of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles A have sulfonic monomeric unit containing ratio be 9.8%, sulfonic containing ratio be 3.82%, acrylonitrile monomer unit containing ratio be 14.0%, (methyl) acrylate monomeric units be 76.2% containing ratio.
The making > of < acrylic polymer particles B
Ion exchange water 300 parts, n-butyl acrylate 80.6 parts, acrylonitrile 14.9 parts, glycidyl methacrylate 4.5 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles B of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles B have the monomeric unit of epoxy radicals containing ratio be 4.5%, epoxy radicals containing ratio be 1.36%, acrylonitrile monomer unit containing ratio be 14.9%, (methyl) acrylate monomeric units containing ratio be 80.6%.
(embodiment 10)
Replace the acrylic polymer particles A obtained in the operation (4) of embodiment 1, use following acrylic polymer particles A.In addition, replace the acrylic polymer particles B obtained in the operation (5) of embodiment 1, use following acrylic polymer particles B.Use this acrylic polymer particles A and this acrylic polymer particles B to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
In addition, the acrylic polymer particles A in perforated membrane slurry relative to the weight ratio (acrylic polymer particles A/ acrylic polymer particles B) of acrylic polymer particles B be 1, sulfonic group in adhesive is 1.8 relative to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making > of < acrylic polymer particles A
Ion exchange water 300 parts, n-butyl acrylate 83.6 parts, acrylonitrile 15.4 parts, 2-acrylamide-2-methyl propane sulfonic 1.0 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles A of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles A have sulfonic monomeric unit containing ratio be 1.0%, sulfonic containing ratio be 0.39%, acrylonitrile monomer unit containing ratio be 15.4%, (methyl) acrylate monomeric units be 83.6% containing ratio.
The making > of < acrylic polymer particles B
Ion exchange water 300 parts, n-butyl acrylate 83.9 parts, acrylonitrile 15.4 parts, glycidyl methacrylate 0.7 part and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles B of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles B have the monomeric unit of epoxy radicals containing ratio be 0.7%, epoxy radicals containing ratio be 0.21%, acrylonitrile monomer unit containing ratio be 15.4%, (methyl) acrylate monomeric units containing ratio be 83.9%.
(embodiment 11)
Replace the acrylic polymer particles A obtained in the operation (4) of embodiment 1, use following acrylic polymer particles A.In addition, replace the acrylic polymer particles B obtained in the operation (5) of embodiment 1, use following acrylic polymer particles B.Use this acrylic polymer particles A and this acrylic polymer particles B to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
In addition, the acrylic polymer particles A in perforated membrane slurry relative to the weight ratio (acrylic polymer particles A/ acrylic polymer particles B) of acrylic polymer particles B be 1, sulfonic group in adhesive is 1.5 relative to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making > of < acrylic polymer particles A
Ion exchange water 300 parts, n-butyl acrylate 77.9 parts, acrylonitrile 14.4 parts, 2-acrylamide-2-methyl propane sulfonic 7.7 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles A of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles A have sulfonic monomeric unit containing ratio be 7.7%, sulfonic containing ratio be 3.00%, acrylonitrile monomer unit containing ratio be 14.4%, (methyl) acrylate monomeric units be 77.9% containing ratio.
The making > of < acrylic polymer particles B
Ion exchange water 300 parts, n-butyl acrylate 78.7 parts, acrylonitrile 14.5 parts, glycidyl methacrylate 6.8 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles B of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles B have the monomeric unit of epoxy radicals containing ratio be 6.8%, epoxy radicals containing ratio be 2.06%, acrylonitrile monomer unit containing ratio be 14.5%, (methyl) acrylate monomeric units containing ratio be 78.7%.
(embodiment 12)
Replace the non-conductive particle obtained in operation (1) ~ (3) of embodiment 1, following non-conductive particle is used to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
The manufacture > of < seeding polymerization composition granule C
The aqueous dispersion of the seeding polymerization composition granule B that the operation (2) putting into embodiment 1 in the reactor with mixer obtains with solid constituent benchmark (i.e. seeding polymerization composition granule B weight basis) count 2 parts, neopelex 0.2 part, potassium peroxydisulfate 0.5 part and ion exchange water 100 parts, mix, obtain mixture, be warming up to 80 DEG C.On the other hand, in another container, benzene mixed ethene 97 parts, methacrylic acid 3 parts, tertiary lauryl mercaptan 4 parts, neopelex 0.5 part and ion exchange water 100 parts, prepare the dispersion of monomer mixture.Through 4 hours the dispersion of this monomer mixture to be added on continuously in said mixture and to be polymerized.The temperature of the reaction system in the continuous print adding procedure of the dispersion of monomer mixture remains 80 DEG C, reacts.After continuous interpolation terminates, at 90 DEG C, continue reaction 3 hours further.
Thus, the aqueous dispersion of the seeding polymerization composition granule C of average grain diameter 400nm is obtained.
The manufacture > of the non-conductive particle of <
Replace the seeding polymerization composition granule B obtained in the operation (2) of embodiment 1, use above-mentioned seeding polymerization composition granule C to carry out the operation same with the operation of embodiment 1 (3), obtain the aqueous dispersion of the non-conductive particle of average grain diameter 700nm.Use the heat resisting temperature (T10 value) of the composition of the monomer (styrene, methacrylic acid, divinylbenzene and vinyl xylene, ethyl vinyl benzene) used till non-conductive particle and non-conductive particle, average circularity and domain size distribution as shown in table 1 from being formed to of seed polymer.
(embodiment 13)
Replace the non-conductive particle obtained in operation (1) ~ (3) of embodiment 1, following non-conductive particle is used to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
The manufacture > of the non-conductive particle of <
Replace the monomer mixture used in the operation (3) of embodiment 1, use 72 parts, mixture (monomer mixing ratio: divinylbenzene/vinyl xylene, ethyl vinyl benzene=82/18, chemical company of Nippon Steel system, goods name: DVB-810) and the methyl methacrylate 18 parts of divinylbenzene and vinyl xylene, ethyl vinyl benzene, in addition, carry out the operation same with the operation of embodiment 1 (3), obtain the aqueous dispersion of the non-conductive particle of average grain diameter 400nm.From seeding polymerization composition granule be formed to obtain non-conductive particle till the heat resisting temperature (T10 value) of the composition of monomer (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and methyl methacrylate) that uses and non-conductive particle, average circularity and domain size distribution as shown in table 1.
(embodiment 14)
The making > of the NMP dispersion of the non-conductive particle of <
After in the aqueous dispersion 100 parts (solid component concentration is 20%) of the non-conductive particle obtained in the operation (3) of embodiment 1, interpolation METHYLPYRROLIDONE (NMP) 200 parts also fully mixes, under 90 DEG C of reduced pressure atmosphere, distill the water in removing system and NMP, obtain the NMP dispersion (solid component concentration is 20%) of non-conductive particle.
The making > of the NMP dispersion of < acrylic polymer particles A
After the middle NMP adding 760 parts of the aqueous dispersion 100 parts (solid constituent is 40%) of the acrylic polymer particles A obtained in the operation (4) of embodiment 1 also fully mixes, under 90 DEG C of reduced pressure atmosphere, distill the water in removing system and NMP, obtain the NMP dispersion (solid constituent is 10%) of acrylic polymer particles A.
The making > of the NMP dispersion of < acrylic polymer particles B
After the middle NMP adding 760 parts of the aqueous dispersion 100 parts (solid constituent is 40%) of the acrylic polymer particles B obtained in the operation (5) of embodiment 1 also fully mixes, under 90 DEG C of reduced pressure atmosphere, distill the water in removing system and NMP, obtain the NMP dispersion (solid constituent is 10%) of acrylic polymer particles B.
The manufacture > of < perforated membrane slurry
By the NMP dispersion of the non-conductive particle obtained in above-mentioned operation, the NMP dispersion of acrylic polymer particles A and, the NMP dispersion of acrylic polymer particles B mixes than for the mode of 87.0:6.5:6.5 with solid constituent, obtains the perforated membrane slurry of solid component concentration 18%.
In addition, the acrylic polymer particles A in perforated membrane slurry relative to the weight ratio (acrylic polymer particles A/ acrylic polymer particles B) of acrylic polymer particles B be 1, sulfonic group in adhesive is 1.7 relative to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
< is with the manufacture > of the negative pole of perforated membrane
The one side of the negative electrode active material layer side of the negative pole obtained in the operation (8) of embodiment 1 is coated with the perforated membrane slurry obtained in above-mentioned operation and obtain pulp layer thus make it cover negative electrode active material layer completely, dried perforated membrane thickness is 5 μm.By pulp layer at 100 DEG C dry 10 minutes, form perforated membrane, obtain the negative pole being with perforated membrane.The negative pole of the band perforated membrane obtained has the such Rotating fields of (perforated membrane)/(negative electrode active material layer)/(Copper Foil).The uniformity of the perforated membrane of the negative pole of the band perforated membrane obtained and reliability, powder falling are evaluated.Show the result in table 1.
< has the manufacture > of the secondary cell of the negative pole of band perforated membrane
Replace the organic dividing plate of band perforated membrane obtained in the operation (9) of embodiment 1, use organic dividing plate (the polypropylene dividing plate of individual layer, the porosity 55%, thickness 25 μm, identical with the dividing plate being used as organic dividing plate in the operation (9) of embodiment 1).
In addition, replace the negative pole obtained in the operation (8) of embodiment 1, use the negative pole of above-mentioned band perforated membrane, in addition, carry out operation similarly to Example 1, obtain secondary cell and evaluate.Show the result in table 1.In addition, when the negative pole of the band perforated membrane by circle is positioned in exterior package container, it loads towards the one side of organic bulkhead sides of circle, Copper Foil side towards the mode of upside with the one side of perforated membrane side.
(comparative example 1)
Replace acrylic polymer particles A, B of obtaining in the operation (4) of embodiment 1, (5), following acrylic polymer particles C is used to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
The making > of < acrylic polymer particles C
Ion exchange water 300 parts, n-butyl acrylate 81.5 parts, acrylonitrile 15.0 parts, 2-acrylamide-2-methyl propane sulfonic 2.0 parts, glycidyl methacrylate 1.5 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles C of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In addition, acrylic polymer particles C has sulfonic group and epoxy radicals, in acrylic polymer particles C sulfonic containing ratio be 0.78%, epoxy radicals containing ratio be 0.45%.
(comparative example 2)
Do not use the acrylic polymer particles A obtained in the operation of embodiment 1 (4), replace the acrylic polymer particles B obtained in the operation (5) of embodiment 1, following acrylic polymer particles B is used to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
The making > of < acrylic polymer particles B
Ion exchange water 300 parts, n-butyl acrylate 78.7 parts, acrylonitrile 14.5 parts, glycidyl methacrylate 6.8 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles B of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles B have the monomeric unit of epoxy radicals containing ratio be 6.8%, epoxy radicals containing ratio be 2.06%, acrylonitrile monomer unit containing ratio be 14.5%, (methyl) acrylate monomeric units containing ratio be 78.7%.
(comparative example 3)
Do not use the acrylic polymer particles B obtained in the operation of embodiment 1 (5), replace the acrylic polymer particles A obtained in the operation (4) of embodiment 1, following acrylic polymer particles A is used to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.
The making > of < acrylic polymer particles A
Ion exchange water 300 parts, n-butyl acrylate 78.7 parts, acrylonitrile 14.5 parts, 2-acrylamide-2-methyl propane sulfonic 6.8 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles A of average grain diameter 0.18 μm.In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles A have sulfonic monomeric unit containing ratio be 6.8%, sulfonic containing ratio be 2.65%, acrylonitrile monomer unit containing ratio be 14.5%, (methyl) acrylate monomeric units be 78.7% containing ratio.
(comparative example 4)
Replace the acrylic polymer particles A obtained in the operation (4) of embodiment 1, following acrylic polymer particles A is used to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.In addition, acrylic polymer particles B uses the particle same with the acrylic polymer particles B obtained in the operation (5) of embodiment 1.
The making > of < acrylic polymer particles A
Ion exchange water 300 parts, n-butyl acrylate 84.5 parts, acrylonitrile 15.5 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles A of average grain diameter 0.18 μm.
In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.In acrylic polymer particles A have sulfonic monomeric unit containing ratio be 0%, sulfonic containing ratio be 0%, acrylonitrile monomer unit containing ratio be 15.5%, (methyl) acrylate monomeric units be 84.5% containing ratio.
(comparative example 5)
Replace the acrylic polymer particles B obtained in the operation (5) of embodiment 1, following acrylic polymer particles B is used to manufacture perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain being with organic dividing plate of perforated membrane and secondary cell and evaluate.Show the result in table 1.In addition, acrylic polymer particles A uses the particle same with the acrylic polymer particles A obtained in the operation (4) of embodiment 1.
The making > of < acrylic polymer particles B
Ion exchange water 300 parts, n-butyl acrylate 84.5 parts, acrylonitrile 15.5 parts and the tertiary lauryl mercaptan 0.05 part as molecular weight regulator, the potassium peroxydisulfate 0.3 part as polymerization initiator, neopelex 1.0 parts as emulsifying agent is put in the autoclave of band mixer, after abundant stirring, be heated to 70 DEG C be polymerized, obtain the aqueous polymer dispersion containing unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 DEG C, after pH is adjusted to 7 by interpolation ammoniacal liquor wherein, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particles B of average grain diameter 0.18 μm.
In addition, the polymerisation conversion obtained by solid component concentration is approximately 99%.
In acrylic polymer particles B have the monomeric unit of epoxy radicals containing ratio be 0%, epoxy radicals containing ratio be 0%, acrylonitrile monomer unit containing ratio be 15.5%, (methyl) acrylate monomeric units containing ratio be 84.5%.
(comparative example 6)
Except acrylic polymer particles A, B of replacing obtaining in the operation (4) of embodiment 2, (5), the acrylate copolymer C obtained in comparative example 1 is used to manufacture beyond perforated membrane slurry, carry out operation similarly to Example 2, obtain being with the negative pole of perforated membrane and secondary cell and evaluate.Show the result in table 1.
According to the result of table 1, can describe as follows.
Use comprises the balancing good of the uniformity of the perforated membrane of the secondary battery separator with secondary cell perforated membrane, electrode for secondary battery and the secondary cell that the secondary cell perforated membrane slurry (embodiment 1 ~ 14) that forms (this adhesive comprises the acrylic polymer particles B having sulfonic acrylic polymer particles A and have epoxy radicals) containing the non-conductive particle of organic macromolecule and adhesive is formed, reliability, cycle characteristics.
On the other hand, be used in there is in a polymer beads sulfonic group and epoxy radicals adhesive case (comparative example 1,6), use the situation (comparative example 2,4) without sulfonic adhesive and use not there is the adhesive of epoxy radicals situation (comparative example 3,5) under, the balanced differences of the uniformity of perforated membrane, reliability, cycle characteristics.

Claims (12)

1. a secondary cell perforated membrane slurry, it comprises containing the non-conductive particle of organic macromolecule, adhesive and solvent,
This adhesive contains:
There is sulfonic acrylic polymer particles A, and
There is the acrylic polymer particles B of epoxy radicals,
When heating with programming rate 10 DEG C/min under nitrogen atmosphere with thermobalance, the temperature that the loss of weight ratio of described non-conductive particle reaches 10 quality % is more than 250 DEG C,
The average grain diameter of this non-conductive particle is 0.1 ~ 2.0 μm,
The average circularity of this non-conductive particle is 0.900 ~ 0.995.
2. secondary cell perforated membrane slurry according to claim 1, wherein,
Relative to all solids composition 100 quality %, described non-conductive particle containing ratio be 70 ~ 97 quality %, described adhesive containing ratio be 0.5 ~ 20 quality %.
3. secondary cell perforated membrane slurry according to claim 1 and 2, wherein,
Described acrylic polymer particles A and described acrylic polymer particles B contains (methyl) acrylonitrile monomer unit and (methyl) acrylate monomeric units.
4. secondary cell perforated membrane slurry according to claim 3, wherein,
In described acrylic polymer particles A and described acrylic polymer particles B, (methyl) acrylonitrile monomer unit in polymer beads containing ratio be 2.5 ~ 40 quality %, (methyl) acrylate monomeric units in polymer beads containing ratio be 60 ~ 97.5 quality %.
5. secondary cell perforated membrane slurry according to claim 1 and 2, wherein,
Described acrylic polymer particles A is 0.3 ~ 3 relative to the weight ratio of described acrylic polymer particles B and acrylic polymer particles A/ acrylic polymer particles B.
6. secondary cell perforated membrane slurry according to claim 1 and 2, wherein,
In described acrylic polymer particles A sulfonic containing ratio be 0.04 ~ 5.8 quality %, the epoxy radicals in described acrylic polymer particles B containing ratio be 0.03 ~ 3.0 quality %.
7. secondary cell perforated membrane slurry according to claim 1 and 2, wherein,
In described adhesive, the sulfonic group in described acrylic polymer particles A is 0.2 ~ 3 relative to the weight ratio of the epoxy radicals in described acrylic polymer particles B and sulfonic group/epoxy radicals.
8. a secondary cell perforated membrane, it is by being formed as membranaceous and dry and obtain by the secondary cell perforated membrane slurry according to any one of claim 1 ~ 7.
9. an electrode for secondary battery, it comprises:
Collector body,
Electrode active material layer, it is attached to this collector body and contains electrode active material and binding agent for electrode, and
Be stacked in the secondary cell perforated membrane according to claim 8 on this electrode active material layer surface.
10. a secondary battery separator, it comprises:
Organic dividing plate,
Be stacked in the secondary cell perforated membrane according to claim 8 on this organic dividing plate.
11. 1 kinds of secondary cells, it comprises:
Positive pole, negative pole, organic dividing plate and electrolyte, wherein,
Any superimposed layer in described positive pole, negative pole and organic dividing plate is had the right the secondary cell perforated membrane described in requirement 8.
The manufacture method of 12. 1 kinds of secondary cell perforated membranes, it comprises:
Basis material is coated with the secondary cell perforated membrane slurry according to any one of claim 1 ~ 7, then carries out dry operation.
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