CN103262297A - 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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CN103262297A
CN103262297A CN2011800576769A CN201180057676A CN103262297A CN 103262297 A CN103262297 A CN 103262297A CN 2011800576769 A CN2011800576769 A CN 2011800576769A CN 201180057676 A CN201180057676 A CN 201180057676A CN 103262297 A CN103262297 A CN 103262297A
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perforated membrane
acrylic polymer
polymer particle
secondary cell
particle
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CN103262297B (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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

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, it is high and can help the secondary cell perforated membrane slurry of secondary cell perforated membrane of improvement of the cycle characteristics of battery to relate to a kind of surface for the manufacture of the electrode that is formed at lithium rechargeable battery or dividing plate, reliability.In addition, the present invention relates to a kind of electrode for secondary battery, secondary battery separator and secondary cell that possesses this secondary cell perforated membrane.
Background technology
In the battery of practicability, lithium rechargeable battery shows the highest energy density, and particularly the miniaturized electronicss that are used for are used more.In addition, except small-sized purposes, also expectation uses in the automobile.Wherein, the long lifetime of expectation lithium rechargeable battery and the further raising of fail safe.
Lithium rechargeable battery in order to prevent the short circuit between positive pole and the negative pole, uses the organic dividing plates of polyolefin such as polyethylene and polypropylene usually.Because the organic dividing plate of polyolefin has rerum natura in fusion below 200 ℃, therefore, at battery because inner and or the stimulation of outside become under the situation of high temperature, cause the contraction of organic dividing plate or fusion etc., the volume of organic dividing plate changes.Its result might cause the short circuit of positive pole and negative pole, owing to emitting of electric energy etc. sets off an explosion etc.
Such owing to the problem of using the organic dividing plate of polyolefin to cause in order to solve, proposed on the organic dividing plate of polyolefin or electrode (negative or positive electrode) superimposed layer contains the layer (perforated membrane) of non-conductive particle such as inorganic particle.And then the thermal runaway that causes for the abnormal response that prevents battery proposes to have and contains Yin Re and the perforated membrane of the polymer beads of fusion or the polymer beads that rises because of the swellbility of heat in electrolyte.It is generally acknowledged, in the temperature of secondary cell because under the situation of short circuit etc. and abnormal ascending, has following function: owing to this melting of polymer pellets or swelling are stopped up fine space in the perforated membrane, stop interelectrode ion to pass through, cause breaking current thus, suppress further temperature rising (cutting off (shut down) function).
For example in patent documentation 1, record a kind of perforated membrane that contains the heat-resistant resin particulate in order to improve fail safe and have the machine particulate that cuts off function.In addition, record use ethylene-vinyl acetate polymer as the perforated membrane adhesive.
Record a kind of method in patent documentation 2, described method prevents that as adhesive inorganic filler is from the powder that falls of perforated membrane by the water dispersible acrylic polymer particle that will have hydrophilic radical such as sulfonic acid.In addition, record by in water dispersible acrylic polymer particle, further having crosslinkable groups, can have tough and tensile and soft perforated membrane.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-139978 communique
Patent documentation 2: open WO2009/123168 number of international monopoly
Summary of the invention
The problem that invention will solve
Yet, according to the inventor's research, the perforated membrane of record is owing to being used as adhesive with the ethylene-vinyl acetate polymer, therefore in the patent documentation 1, be used to form the dispersed insufficient of heat-resistant resin particulate in the slurry of this perforated membrane and organic fine particles, the lack of homogeneity of perforated membrane.Its result can't make perforated membrane have full intensity and cut-out function sometimes.In addition, as can be known, though the excellent dispersion of the inorganic filler in the patent documentation 2 in the perforated membrane perforated membrane slurry of record, but in the acrylic polymer particle as adhesive, contain under the situation of hydrophilic radical and crosslinkable groups, have and have reactive functional group mutually, therefore, there is the tendency that causes cross-linking reaction in the slurry manufacturing process.Therefore, the screening characteristics of passing slurry in time becomes unstable, and as a result of, the uniformity of perforated membrane and intensity become insufficient sometimes.
Therefore, the objective of the invention is to, a kind of secondary cell perforated membrane slurry manufacturing of using the excellent dispersion of screening characteristics and non-conductive particle is provided, can improve cycle characteristics and uniformity and the high secondary cell perforated membrane of intensity of the secondary cell that obtains.In addition, its purpose is, a kind of good electrode for secondary battery of function and secondary battery separator of cutting off is provided.
Therefore, the inventor etc. concentrate on studies, and found that, by importing sulfonic group and epoxy radicals and they form with blend material respectively in the acrylic polymer particle as adhesive, can improve uniformity and the intensity of perforated membrane.In brief, by using specific adhesive, the cross-linking reaction in the slurry manufacturing process can be suppressed, the tackify of slurry etc. can be reduced.Therefore, the dispersiveness of the non-conductive particle in the perforated membrane slurry and the screening characteristics of perforated membrane slurry can be improved, the high perforated membrane of uniformity and intensity can be obtained.In addition, the inventor finds, the dispersiveness by improving the non-conductive particle in the perforated membrane slurry and the screening characteristics of perforated membrane slurry except the productivity ratio of perforated membrane, use the cycle characteristics of the secondary cell of this perforated membrane also to be improved.
For the method for dealing with problems
Be that the purport of the present invention of purpose is as described below to solve such problem.
(1) a kind of secondary cell perforated membrane slurry, it comprises and contains the non-conductive particle of organic macromolecule, adhesive and solvent and form,
This adhesive contains:
Have sulfonic acrylic polymer particle A, and
Acrylic polymer particle B with epoxy radicals.
(2) according to (1) described secondary cell perforated membrane slurry, wherein,
With respect to all solids composition 100 quality %, the ratio that contains of described non-conductive particle is 70～97 quality %, and the ratio that contains of described adhesive is 0.5～20 quality %.
(3) according to (1) or (2) described secondary cell perforated membrane slurry, wherein,
Described acrylic polymer particle A and described acrylic polymer particle B contain (methyl) acrylonitrile monemer unit and (methyl) acrylate monomeric units forms.
(4) according to (3) described secondary cell perforated membrane slurry, wherein,
In described acrylic polymer particle A and described acrylic polymer particle B, the ratio that contains of (methyl) acrylonitrile monemer unit in the polymer beads is 2.5～40 quality %, and the ratio that contains of (methyl) acrylate monomeric units in the polymer beads is 60～97.5 quality %.
(5) according to each described secondary cell perforated membrane slurry in (1)～(4), wherein,
Described acrylic polymer particle A is 0.3～3 with respect to the weight ratio (acrylic polymer particle A/ acrylic polymer particle B) of described acrylic polymer particle B.
(6) according to each described secondary cell perforated membrane slurry in (1)～(5), wherein,
The sulfonic ratio that contains among the described acrylic polymer particle A is 0.04～5.8 quality %, and the ratio that contains of the epoxy radicals among the described acrylic polymer particle B is 0.03～3.0 quality %.
(7) according to each described secondary cell perforated membrane slurry in (1)～(6), wherein,
In described adhesive, the sulfonic group among the described acrylic polymer particle A is 0.2～3 with respect to the weight ratio (sulfonic group/epoxy radicals) of the epoxy radicals among the described acrylic polymer particle B.
(8) according to each described secondary cell perforated membrane slurry in (1)～(7), wherein,
Under blanket of nitrogen during with the heating of 10 ℃/minute of programming rates, the temperature that the loss of weight ratio of described non-conductive particle reaches 10 quality % is more than 250 ℃ with thermobalance,
The average grain diameter of this non-conductive particle is 0.1～2.0 μ m,
The average circularity of this non-conductive particle is 0.900～0.995.
(9) a kind of secondary cell perforated membrane, it is by forming membranaceous and dry obtaining with each described secondary cell perforated membrane slurry in above-mentioned (1)～(8).
(10) a kind of 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 described secondary cell perforated membrane of this electrode active material layer lip-deep (9).
(11) a kind of secondary battery separator, it comprises:
Organic dividing plate,
Be stacked in (9) the described secondary cell perforated membrane on this organic dividing plate.
(12) a kind of 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 (9) described secondary cell perforated membrane.
(13) a kind of manufacture method of secondary cell perforated membrane, it comprises:
Each described secondary cell perforated membrane slurry in basis material coating above-mentioned (1)～(8) carries out dry operation then.
The invention effect
According to the present invention, a kind of secondary cell perforated membrane slurry can be provided, described secondary cell perforated membrane slurry is by containing the adhesive that non-conductive particle and characteristic are formed, thereby for the manufacture of uniformity and excellent strength, can be conducive to the secondary cell perforated membrane of the cycle characteristics of secondary cell.In addition, the dispersiveness of this perforated membrane slurry and screening characteristics excellence.And then, be stacked on the surface of electrode or organic dividing plate by the secondary cell perforated membrane that will use this perforated membrane slurry manufacturing, prevent the disengaging (mealiness that falls (powder fall Chi) of non-conductive particle and electrode active material) and cut off function (reliability) excellence.
Embodiment
Below, to (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 describe successively.
(1) secondary cell perforated membrane slurry
Secondary cell perforated membrane slurry of the present invention (below, be expressed as " perforated membrane slurry " sometimes.) for being used to form the slurry of secondary cell perforated membrane described later.The perforated membrane slurry contains the adhesive of non-conductive particle and characteristic composition, and will reaching arbitrarily as this non-conductive particle, this adhesive of solid constituent, composition be evenly dispersed in the solvent described later.
(non-conductive particle)
Be used for non-conductive particle of the present invention and contain organic polymer.In the present invention, contain the non-conductive particle of organic macromolecule by use, can reduce to the performance of secondary cell cause dysgenic metal pollution (below, be expressed as " metal impurities " sometimes.), and can suppress the manufacturing cost of secondary cell perforated membrane slurry.
Non-conductive particle preferably contains the divinylbenzene monomeric unit.The divinylbenzene monomeric unit of the total monomer weight in the non-conductive particle contain ratio be preferably 20～80 quality %, more preferably 25～70 quality %, be preferably 30～60 quality % especially.Be made as above-mentioned scope by the ratio that contains with the divinylbenzene monomeric unit, 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 that obtains also improves.
Non-conductive particle preferably further contains the 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 the non-conductive particle is preferably 3.2～48 quality %, 10～40 quality % more preferably.Be made as above-mentioned scope by the ratio that contains with the vinyl xylene, ethyl vinyl benzene monomeric unit, become well with the caking property of adhesive described later, and the flexibility of the secondary cell perforated membrane that obtains become good.In addition, made under the situation of electrode for secondary battery in that this secondary cell perforated membrane is stacked in electrode, can prevent the disengaging (powder falls) of electrode active material.Its result has used the secondary cell of this secondary cell perforated membrane to show excellent cycle characteristics.
Contained divinylbenzene monomeric unit and the content of vinyl xylene, ethyl vinyl benzene monomeric unit are preferably 1.0～5.25 than (divinylbenzene/vinyl xylene, ethyl vinyl benzene) in the non-conductive particle, and more preferably 1.25～5.00, be preferably 1.25～4.75 especially.Be made as above-mentioned scope by the content ratio with divinylbenzene monomeric unit contained in the non-conductive particle and vinyl xylene, ethyl vinyl benzene monomeric unit, 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 that obtains and intensity improve.In addition, under the situation of making electrode for secondary battery, can prevent the disengaging (powder falls) of electrode active material, therefore, use the secondary cell of this secondary cell perforated membrane to show excellent cycle characteristics.
Non-conductive particle preferably contains the monomer of polar functionalities except above-mentioned 2 kinds of monomeric units.
The monomer of polar functionalities in molecular structure, contain polar group and can with the monomer of divinylbenzene and vinyl xylene, ethyl vinyl benzene copolymerization.Polar group refers to the functional group that can dissociate or the functional group with polarization in water, particularly, can enumerate: carboxyl, sulfonic group, hydroxyl, amide groups, cationic group, 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-acetoxyl group acrylic 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: maleic acid methyl allyl ester, maleic acid diphenyl ester, maleic acid nonyl ester, maleic acid decyl ester, maleic acid dodecyl ester, maleic acid stearyl, and maleate such as 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 ethyl ester, 2-acrylamide-2-methyl propane sulfonic acid, 3-allyl oxygen-2-hydroxy-propanesulfonic acid etc.
As the monomer of hydroxyl, can enumerate: ethene unsaturated alcohols such as (methyl) allyl alcohol, 3-butene-1-alcohol, 5-hexen-1-ol; The chain triacontanol ester class of ethene unsaturated carboxylic acids such as 2-Hydroxy ethyl acrylate, acrylic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, maleic acid two-2-hydroxy methacrylate, maleic acid two-4-hydroxyl butyl ester, itaconic acid two-2-hydroxy propyl ester; General formula CH 2=CR 1-COO-(C nH 2nO) m(m represents that 2～9 integer, n represent 2～4 integer, R to-H 1Expression hydrogen or methyl) shown in PAG and (methyl) acrylic acid ester class; List (methyl) esters of acrylic acid of the dihydroxy ester of 2-hydroxyethyl-2 '-(methyl) acryloxy phthalic acid ester, 2-hydroxyethyl-2 '-dicarboxylic acids such as (methyl) acryloxy succinate; Vinyl ethers such as 2-hydroxyethyl vinyl ethers, 2-hydroxypropyl vinyl ethers; List (methyl) allyl ether series of (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-aklylene glycols such as 6-hydroxyl hexyl ether; Polyether polyols (methyl) mono allyl ether classes such as diethylene glycol list (methyl) allyl ether, DPG list (methyl) allyl ether; Glycerine list (methyl) allyl ether, (methyl) pi-allyl-2-chloro-3-hydroxypropyl ether, (methyl) pi-allyl-2-hydroxyl-halogen of (gathering) aklylene glycols such as 3-chloropropyl ether and list (methyl) allyl ether of hydroxyl substituent; The list of polyhydric phenols such as eugenol, isoeugenol (methyl) allyl ether and halogen substituent thereof; (methyl) allyl sulfide ethers of (methyl) pi-allyl-2-hydroxyethyl thioether, (methyl) pi-allyl-aklylene glycols such as 2-hydroxypropyl thioether etc.
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) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid dimethylamino propyl ester etc.
As the monomer of cyano-containing, can enumerate: acrylonitrile compounds such as acrylonitrile, methacrylonitrile.
As the monomer that contains epoxy radicals, can enumerate: glycidyl acrylate, glycidyl methacrylate etc.
As the salt of the monomer of the group monomer of the monomer of carboxylic monomer, the monomer that contains sulfonic monomer, hydroxyl, amide-containing, cation and cyano-containing, can enumerate: by alkali metal salts such as above-named monomer and the sodium salt that can constitute with the suitable ion of their combinations, sylvite; Alkali salt such as calcium salt, magnesium salts; Organic amine salts such as ammonium salt, monoethanolamine salt, triethanolamine salt etc.
As the monomer of polar functionalities, the monomer of preferred carboxylic monomer, amide-containing, preferred especially acrylic acid, methacrylic acid, itaconic acid, acrylamide.
The ratio that contains of the monomer of the polar functionalities of the total monomer weight in the non-conductive particle is preferably 0.05～4 quality %, and more preferably 0.1～3 quality % is preferably 0.2～2 quality % especially.If not the ratio that contains of the monomer of the polar functionalities of the total monomer weight in the conductive particle is above-mentioned scope, the water content of then excellent dispersion, and non-conductive particle surface is few, therefore, shows excellent cycle characteristics.
Non-conductive particle also can contain monomeric unit arbitrarily except above-mentioned 3 kinds of monomeric units.As monomer arbitrarily, can enumerate: polynary (methyl) acrylate compounds, aromatic series mono-vinyl compound, (methyl) acrylate monomer, conjugate diene monomer, vinyl esters compound, alpha-olefin compound.These monomers can contain more than 2 kinds in non-conductive particle.
As polynary (methyl) acrylate compounds, can enumerate: polyethyleneglycol diacrylate, 1,3-butanediol diacrylate, 1,6-hexanediyl ester, neopentylglycol diacrylate, polypropyleneglycol diacrylate, 2,2 '-two (4-acryloxy propoxyl group phenyl) propane, 2, diacrylate ester compounds such as 2 '-two (4-acryloxy diethoxy phenyl) propane; Triacrylate compounds such as trimethylolpropane triacrylate, trimethylolethane trimethacrylate acrylate, tetramethylol methane triacrylate; Tetraacrylate compounds such as tetramethylol methane tetraacrylate; Ethylene glycol dimethacrylate, diethylene glycol dimethylacrylate, triethylene glycol dimethylacrylate, polyethylene glycol dimethacrylate, 1,3-butanediol dimethylacrylate, 1,4-butanediol dimethylacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol dimethacrylate, DPG dimethylacrylate, polypropylene glycol dimethacrylate, 2, dimethylacrylate compounds such as 2 '-two (4-methacryloxy diethoxy phenyl) propane; Trimethyl acrylic ester compounds such as trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methacrylate etc.Wherein, preferably use ethylene glycol dimethacrylate or trimethylol-propane trimethacrylate.
As aromatic series mono-vinyl 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 aminoethyl ester etc.
As methacrylate monomer, can enumerate: butyl methacrylate, methacrylic acid 2-Octyl Nitrite, methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid N, N '-dimethyl aminoethyl methyl ester etc.
As conjugate diene monomer, can enumerate: butadiene, isoprene etc.
As the vinyl esters compound, can enumerate: vinylacetate etc.
As the alpha-olefin compound, can enumerate: 4-methyl-1-pentene etc.
Above-mentioned monomer arbitrarily can use wantonly a kind or be used in combination more than 2 kinds separately.In the above-mentioned monomer arbitrarily, particularly from considering optimization styrene, methyl methacrylate or their combination with reactive viewpoint of divinylbenzene and vinyl xylene, ethyl vinyl benzene.
The ratio that contains of the monomeric unit arbitrarily of the total monomer weight in the non-conductive particle is preferably 3～80 quality %, and more preferably 4～70 quality % are preferably 5～60 quality % especially.Particularly containing under styrene and/or the methyl methacrylate situation as monomer arbitrarily, it preferably contains ratio is that benchmark is 4.5～76.5 quality % with the monomer total amount that constitutes non-conductive particle.Containing under both situations of styrene and methyl methacrylate, preferably their total content is this scope.Be made as below the 76.5 quality % by the ratio that contains with styrene and/or methyl methacrylate, can improve the thermal endurance of non-conductive particle, can improve the thermal endurance of perforated membrane, and then can reduce the generation of the short circuit of battery under the high temperature.On the other hand, be made as more than the 4.5 quality % by the ratio that contains with styrene and/or methyl methacrylate, can prevent that the dispersiveness of non-conductive particle from reducing, improve the porous film strength, and can also obtain film uniformity.
(manufacture method of non-conductive particle)
The manufacture method of non-conductive particle is not particularly limited, can enumerate following method: will constitute the monomer of non-conductive particle and other composition arbitrarily as required is dissolved or dispersed in the decentralized medium, by emulsion polymerization or soap-free polymerization method, in this dispersion liquid, carry out polymerization.
In emulsion polymerisation, consider that from the aspect of the particle diameter that obtains expecting and average circularity preferably polymerization being divided into a plurality of stages carries out.For example, the part of the monomer by at first will constituting non-conductive particle is carried out polymerization and is formed the seeding polymerization composition granule, next, makes this seeding polymerization composition granule absorb other monomer, under this state, carry out polymerization, can make non-conductive particle (seeding polymerization method).And then when forming the seeding polymerization composition granule, polymerization can be further divided into a plurality of stages carries out.
More specifically, for example can use the part of the monomer that constitutes non-conductive particle to form seeding polymerization composition granule A, other the monomer that uses this seeding polymerization composition granule A and constitute non-conductive particle forms the seeding polymerization composition granule B with bigger particle diameter, and then, use this seeding polymerization composition granule B and constitute the residual monomers of non-conductive particle and other composition arbitrarily as required further forms the non-conductive particle with big particle diameter.
As mentioned above, form the seeding polymerization composition granule by the reaction in 2 stages, further form non-conductive particle then, have thus and can stably obtain the particle diameter expected and the advantage of average circularity.At this moment, part or all (being preferably all) of constituting the monomer of the polar functionalities in the monomer of non-conductive particle used the stability of guaranteeing particle when forming seeding polymerization composition granule A and seeding polymerization composition granule B, so preferred.And then, at this moment, as the monomer that is used to form seeding polymerization composition granule A, use as the styrene of monomer arbitrarily owing to guarantee that when forming seeding polymerization composition granule B and non-conductive particle the seeding polymerization composition granule absorbs the absorbability of monomer, therefore preferred.
Owing to also comprise as above being divided into the situation that a plurality of stages carry out polymerization, therefore, constitute the monomer of non-conductive particle when polymerization, its whole monomer also can not form the state that becomes mixture.Be divided under the situation that a plurality of stages carry out in polymerization, preferably the composition from the monomer of the polymerized unit that constitutes non-conductive particle in the non-conductive particle that finally obtains satisfies the ratio of components of the monomer of the above-mentioned non-conductive particle of formation.
As the medium of the polymerization of the monomer that be used for to constitute non-conductive particle, can enumerate: water, organic solvent and their mixture.As organic solvent, can use for radical polymerization to be combined into inertia and can not to suppress the solvent of the polymerization of monomer.As the concrete example of organic solvent, can enumerate: ketone and their mixtures such as ester class, cyclohexanone such as alcohols such as methyl alcohol, ethanol, propyl alcohol, cyclohexanol, octanol, dibutyl phthalate, dioctyl phthalate.The medium that preferably can make water-baseds such as water carries out emulsion polymerisation as polymerization as decentralized medium.
With regard to their ratio of amount when seeding polymerization composition granule and monomer are reacted, with respect to seeding polymerization composition granule 1 mass parts, the use amount of monomer is preferably 2～19 mass parts, 3～16 mass parts more preferably, further 4～12 mass parts more preferably.By being more than 2 mass parts with respect to the use amount of the monomer of seeding polymerization composition granule 1 mass parts, can improve mechanical strength and the thermal endurance of the non-conductive particle that obtains.In addition, by being below 19 mass parts with respect to the use amount of the monomer of seeding polymerization composition granule 1 mass parts, the seeding polymerization composition granule can absorb monomer efficiently, therefore, the amount of monomer that is not absorbed by the seeding polymerization composition granule can be remained less scope.In addition, owing to can carry out the control of non-conductive particle grain size well, therefore, can prevent to have the big particle of wide in range particle diameter distribution and a large amount of molecules.
As the concrete operation of polymerization, once drop into the method for monomer, the method for carrying out that polymerization separates or adding monomer continuously while have with respect to the water-borne dispersions of seeding polymerization composition granule.Preferred polymeric is initiated and produces in fact in the seeding polymerization composition granule and makes before crosslinked the seeding polymerization composition granule absorb monomer.
If after the mid-term of polymerization, add monomer, then because monomer is not absorbed by the seeding polymerization composition granule, therefore, produce molecule in a large number and make the polymerization stability variation, can't keep polymerization reaction sometimes.Therefore, preferably before polymerization causes, add whole monomers or polymerisation conversion and reach about 30% with respect to the seeding polymerization composition granule before the interpolation of the whole monomers of end.In the water-borne dispersions of seeding polymerization composition granule, add monomer before causing particularly preferably in polymerization and stir, make the seeding polymerization composition granule absorb initiated polymerization behind the described monomer.
In the reaction system of polymerization, except the monomer and decentralized medium that constitute non-conductive particle, can add any composition.Particularly, can add compositions such as polymerization initiator, surfactant, suspension protective agent.As polymerization initiator, can use general water miscible radical polymerization initiator or oil-soluble radical polymerization initiator, but never the monomer that is absorbed by the seeding polymerization composition granule the aqueous phase initiated polymerization few aspect consider, preferably use water miscible radical polymerization initiator.As water miscible radical polymerization initiator, can enumerate: the redox series initiators that is combined to form of potassium peroxydisulfate, sodium peroxydisulfate, hydrogen phosphide cumene, hydrogen peroxide or above-mentioned water soluble starter or reducing agents 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 the oil-soluble radical polymerization initiator, can preferably use peroxidating (2 ethyl hexanoic acid) tert-butyl ester.In addition, in polymerization reaction, if a small amount of water miscible polymerization inhibitors such as potassium bichromate, iron chloride, quinhydrones that add then can suppress the generation of molecule, so preferred.
As surfactant, can use common surfactant, can illustration: for example the anion such as formaldehyde condensation products of neopelex, NaLS, dialkyl sodium sulfosuccinate, naphthalene sulfonic acids be emulsifying agent.And then also can be used in combination nonionics such as polyoxyethylene nonylplenyl ether, polyethyleneglycol hard acid esters, sorbitan list hard acid esters is surfactant.As preferred suspension protective agent, can enumerate: polyvinyl alcohol, carboxymethyl cellulose, Sodium Polyacrylate or micropowder inorganic compound etc.
(proterties of non-conductive particle)
Be used for non-conductive coating of particles of the present invention and be spherical, needle-like, bar-shaped, spindle shape, tabular etc., be not particularly limited, but preferably spherical, needle-like, spindle shape.In addition, as non-conductive particle, also can use porous particles.With respect to all solids composition 100 quality % of perforated membrane slurry, the ratio that contains of non-conductive particle is preferably 70～97 quality %, and more preferably 80～95 quality % are preferably 85～95 quality % especially.By being made as above-mentioned scope with respect to the ratio that contains of the non-conductive particle of all solids composition 100 quality % of perforated membrane slurry, can obtain showing the perforated membrane of high thermal stability.In addition, the non-conductive particle that can be inhibited is from the disengaging (powder falls) of perforated membrane and show high-intensity perforated membrane, can prevent the reduction of battery behaviors such as cycle characteristics simultaneously.
From the viewpoint consideration of perforated membrane being given thermal endurance and improving the reliability of electrode for secondary battery described later and secondary battery separator, preferred non-conductive particle has high-fire resistance.Particularly, the temperature that the loss of weight ratio of the non-conductive particle in the thermobalance analysis under the blanket of nitrogen during with the heating of 10 ℃/minute of programming rates reaches 10 quality % is preferably more than 250 ℃, more preferably more than 300 ℃, is preferably especially more than 360 ℃.On the other hand, the upper limit of this temperature is not particularly limited, and can be made as for example below 450 ℃.
In the present invention, as non-conductive particle, preferably use the content of metal impurities to be the non-conductive particle below the 100ppm.If use the non-conductive particle that contains metal impurities or metal ion morely, then in the perforated membrane slurry, above-mentioned metal impurities or metal ion stripping, it causes polymer and ionomer in the perforated membrane slurry, the perforated membrane slurry condenses, and the result causes the porousness of perforated membrane to reduce.Therefore, might use multiplying power property (output characteristic) variation of the secondary cell of this perforated membrane.As above-mentioned metal, least preferred particularly Ca, Co, Cu, Fe, Mg, Ni, Zn and the Cr etc. of containing.Therefore, as the tenor in the non-conductive particle, be preferably below the 100ppm in the total amount of these metal ions, more preferably below the 50ppm.Above-mentioned content is more few, more is difficult for causing the deterioration of battery behavior.Metal simple-substance or metal ion beyond these said " metal impurities " refer to non-conductive particle.The content of the metal impurities in the non-conductive particle can use ICP (inductively coupled plasma (Inductively Coupled Plasma)) to measure.
The average grain diameter that is used for non-conductive particle of the present invention is preferably 0.1～2 μ m, and more preferably 0.1～1 μ m is preferably 0.1～0.8 μ m especially.Be made as above-mentioned scope by the average grain diameter with non-conductive particle, control the dispersity of perforated membrane slurry easily, therefore, the manufacturing of the perforated membrane of specific thickness uniformly becomes easy.In addition, the particles filled rate that can suppress in the perforated membrane uprises, and therefore, the ionic conductivity that can suppress in the perforated membrane reduces, and can realize excellent cycle characteristics.If making the average grain diameter of non-conductive particle is the scope of 0.1～0.8 μ m, so the controlled excellence in the easiness of then disperseing, being coated with, space is preferred.For average grain diameter, can followingly calculate: carry out electron microscope observation, for the particle more than 100, the longest edge of its particle picture is made as a, minor face is made as b, calculate (a+b)/2, and obtain by its mean value.
The average circularity that is used for non-conductive particle of the present invention is preferably 0.900～0.995, and more preferably 0.91～0.98, be preferably 0.92～0.97 especially.Be made as above-mentioned scope by the average circularity with non-conductive particle, non-conductive particle contact area appropriateness each other can be kept, therefore, can improve porous film strength and thermal endurance.Its result can improve the reliability of the secondary cell that has used this perforated membrane.
In addition, the BET specific area that is used for non-conductive particle of the present invention is considered from the viewpoint of the cohesion that suppresses non-conductive particle and the flowability of optimizing the perforated membrane slurry, particularly, is preferably 0.9～200m 2/ g, more preferably 1.5～150m 2/ g.
Non-conductive particle grain size distribution is preferably 1.00～1.4, and more preferably 1.00～1.3, be preferably 1.00～1.2 especially.By non-conductive particle grain size distribution is made as above-mentioned scope, can between non-conductive particle, keep the space of regulation, therefore, can be suppressed in the secondary cell of the present invention owing to hindering the resistance increase that moving of lithium causes.In addition, after non-conductive particle grain size distribution can use the laser diffraction refraction particle size distribution device (LS230) of Beckman Co., Ltd. system to carry out particle size determination, obtained by the ratio V/N of the volume average particle size V that obtains and number average bead diameter N.
(adhesive)
Be used for adhesive of the present invention and contain the acrylic polymer particle B that has sulfonic acrylic polymer particle A and have epoxy radicals.In the present invention, contain the adhesive of this acrylic polymer particle A and this acrylic polymer particle B by use, can prevent the gelation of perforated membrane slurry, therefore, can form uniform perforated membrane.
Having sulfonic acrylic polymer particle A contains and has sulfonic monomeric unit and form.Particularly, it is characterized in that, in the polymer as acrylic polymer particle A, contain and have sulfonic monomeric unit.
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 ethyl ester, 2-acrylamide-2-methyl propane sulfonic acid, 3-allyl oxygen-2-hydroxy-propanesulfonic acid, Sodium styrene sulfonate etc.
The ratio that contains with sulfonic monomeric unit among the acrylic polymer particle A is preferably 0.3～10 quality %, more preferably 1.3～9 quality %.If the ratio that contains with sulfonic monomeric unit among the acrylic polymer particle A is above-mentioned scope, then can give good caking property to adhesive, can suppress non-conductive particle from the disengaging (powder falls) of perforated membrane.
The sulfonic ratio that contains among the acrylic polymer particle A is preferably 0.04～5.8 quality %, and more preferably 0.1～4 quality % is preferably 0.5～3.5 quality % especially.If the sulfonic ratio that contains among the acrylic polymer particle A is above-mentioned scope, can prevent that then the viscosity of perforated membrane slurry from rising, keep the screening characteristics of perforated membrane slurry well.In addition, have sufficient cohesive force with respect to non-conductive particle, and uprise with the reactivity of the epoxy radicals of acrylic polymer particle B described later.And then, the dispersiveness of the non-conductive particle in the raising perforated membrane slurry.
Acrylic polymer particle A preferably further contains (methyl) acrylonitrile monemer unit except having sulfonic monomeric unit.The ratio that contains of (methyl) acrylonitrile monemer unit among the acrylic polymer particle A is preferably 2.5～40 quality %, and more preferably 3～37 quality % are preferably 5～35 quality % especially.If the ratio that contains of (methyl) acrylonitrile monemer unit among the acrylic polymer particle A is above-mentioned scope, then the intensity of adhesive improves, and therefore, can make the secondary cell with excellent cycle characteristics.
In addition, in the present invention, have sulfonic acrylic polymer particle A except above-mentioned monomeric unit, preferably further contain (methyl) acrylate monomeric units.The ratio that contains of (methyl) acrylate monomeric units among the acrylic polymer particle A is preferably 60～97.5 quality %, and more preferably 62～96 quality % are preferably 65～95 quality % especially.If the ratio that contains of (methyl) acrylate monomeric units among the acrylic polymer particle A is above-mentioned scope, then not stripping and show swellability to the appropriateness of electrolyte in the electrolyte of secondary cell of adhesive, the conductibility that therefore, can keep lithium ion well.Its result.Can improve the cycle characteristics of secondary cell.
As (methyl) acrylate monomer, can enumerate: alkyl acrylates such as methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, acrylic acid pentyl ester, Hexyl 2-propenoate, acrylic acid heptyl ester, 2-ethyl hexyl acrylate, 2-EHA, acrylic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, lauryl acrylate, acrylic acid n-tetradecane base ester, stearyl acrylate ester; Methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, the metering system tert-butyl acrylate, the methacrylic acid pentyl ester, hexyl methacrylate, the metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, methacrylic acid 2-Octyl Nitrite, nonyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, methacrylic acid n-tetradecane base ester, alkyl methacrylates such as methacrylic acid stearyl ester.Wherein, since with the carbon number of the alkyl of non-carbonyl oxygen atom bonding be (methyl) ethyl acrylate of 2～13, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate shows not in electrolyte stripping and the swelling of the appropriateness of electrolyte is brought thus the conductibility of lithium ion, in addition, in the dispersion of active material, be difficult to cause the cross-linked cohesion of polymer, so it is preferred, wherein, preferably with the carbon number of the alkyl of non-carbonyl oxygen atom bonding be (methyl) n-butyl acrylate of 4～10, (methyl) 2-EHA.
And then, acrylic polymer particle A except above-mentioned monomeric unit (have sulfonic monomeric unit, (methyl) acrylonitrile monemer unit, and (methyl) acrylate monomeric units), preferably contain can with other the monomeric unit of their copolymerization.The ratio that contains of the monomeric unit of other among the acrylic polymer particle A is preferably 0.1～10 quality %, more preferably 0.1～5 quality %.If the ratio that contains of the monomeric unit of other among the acrylic polymer particle A is above-mentioned scope, then the dispersiveness of particle can not reduce, and can be formed uniformly perforated membrane.
As other monomer, can enumerate: styrenic monomers such as styrene, chlorostyrene, vinyltoluene, t-butyl styrene, vinyl benzoic acid, vinyl benzoic acid methyl esters, vinyl naphthalene, 1-chloro-4-methyl-benzene, AMS, divinylbenzene; The ethene that acrylic acid, methacrylic acid, crotonic acid, 2-ethylacrylic acid, iso-crotonic acid, α-acetoxyl group acrylic acid, β-trans aryloxy group acrylic acid, α-chloro-β-E-methoxy acrylic acid, β-diaminourea acrylic acid etc. have monocarboxylic acid is unsaturated carboxylic acid; Maleic acid, fumaric acid, itaconic acid, citraconic acid, dimethyl maleic acid, phenyl maleic acid, chloromaleic acid, dichloro-maleic acid, fluoro maleic acid, and ethene with dicarboxylic acids such as maleate be unsaturated carboxylic acid and derivative thereof; Olefines such as ethene, propylene; Diene monomer such as butadiene, isoprene; Halogen atom such as vinyl chloride, vinylidene chloride monomer; Vinyl esters such as vinylacetate, propionate, vinyl butyrate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, isopropenyl vinyl ketone; N-vinyl pyrrolidone, vinylpyridine, vinyl imidazole etc. contain the heterocycle vinyl compound; Acid amides such as acrylamide, N hydroxymethyl acrylamide is monomer etc.In addition, acrylic polymer particle A can only contain a kind of other monomeric unit, also can contain more than 2 kinds with ratio combination arbitrarily.
Acrylic polymer particle B with epoxy radicals contains the monomeric unit with epoxy radicals to form.Particularly, it is characterized in that, in the polymer as acrylic polymer particle B, contain the monomeric unit with epoxy radicals.
As the monomer with epoxy radicals, can enumerate: unsaturated glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, cyclobutenyl glycidyl ether, o-allyl base glycidyl ether; Butadiene monoepoxide, chlorobutadiene monoepoxide, 4,5-epoxy-2-amylene, 3,4-epoxy-1-VCH, 1,2-epoxy-5,9-encircle the monoepoxide of diene such as 12 carbon diene or polyenoid; 3,4-epoxy-1-butylene, 1,2-epoxy-5-hexene, 1,2-epoxy-alkenyl epoxides such as 9-decene; The glycidyl esters class of 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 unsaturated carboxylic acids such as glycidyl esters of 4-methyl-3-cyclohexene carboxylate.Wherein, from because reactive high with sour functional groups, therefore, the caking property of the perforated membrane that obtains is high and the powder that falls is low, used the aspect of cycle characteristics excellence of the battery of perforated membrane to consider, preferred vinyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, most preferably glycidyl acrylate, glycidyl methacrylate.
The ratio that contains of the monomeric unit with epoxy radicals among the acrylic polymer particle B is preferably 0.3～8 quality %, more preferably 0.3～5 quality %.If the ratio that contains of the monomeric unit with epoxy radicals among the acrylic polymer particle B is above-mentioned scope, then can give good caking property to adhesive, can suppress non-conductive particle from the disengaging (powder falls) of perforated membrane.
The ratio that contains of the epoxy radicals among the acrylic polymer particle B is preferably 0.03～3.0 quality %, and more preferably 0.1～2.5 quality % is preferably 0.1～1.5 quality % especially.If the ratio that contains of the epoxy radicals among the acrylic polymer particle B is above-mentioned scope, the viscosity that then can prevent the perforated membrane slurry rises and keeps the screening characteristics of perforated membrane slurry well.In addition, uprise with the sulfonic reactivity of above-mentioned acrylic polymer particle A, therefore, the porous film strength improves.
Acrylic polymer particle B except the monomeric unit with epoxy radicals, preferably further contain (methyl) acrylonitrile monemer unit, (methyl) acrylate monomeric units and can with other the monomeric unit of their copolymerization.(methyl) acrylonitrile monemer unit among the acrylic particles B contain ratio, (methyl) acrylate monomeric units contain ratio and can with their copolymerization other monomeric unit contain among ratio and the above-mentioned acrylic polymer particle A to contain ratio identical.In addition, each monomer can illustration and above-mentioned acrylic polymer particle A in the same monomer of monomer.
Acrylic polymer particle A is preferably 0.3～3 with respect to the weight ratio (acrylic polymer particle A/ acrylic polymer particle B) of acrylic polymer particle B, and more preferably 0.4～3, be preferably 0.5～2 especially.Be above-mentioned scope by making acrylic polymer particle A with respect to the weight ratio of acrylic polymer particle B, can prevent the gelation (viscosity rising) of perforated membrane slurry, make the screening characteristics of perforated membrane slurry good, the porous film strength that obtains improves.
Acrylic polymer particle A and acrylic polymer particle B use under the state of the solution of the dispersion liquid that is scattered in decentralized medium (water or organic solvent) or dissolving (below, be designated as " polymer beads dispersion liquid A " sometimes and reach " polymer beads dispersion liquid B ".)。In the present invention, consider from the viewpoint that viewpoint excellence, the rate of drying of environment are fast, preferably make water as decentralized medium.In addition, under the situation as decentralized medium with an organic solvent, use N-methyl pyrrolidone organic solvents such as (NMP).
Be scattered under the situation of decentralized medium with graininess at acrylic polymer particle A and acrylic polymer particle B, with the acrylic polymer particle A of graininess dispersion and preferred 0.05～0.5 μ m of average grain diameter (dispersion particle diameter) of acrylic polymer particle B, further preferred 0.07～0.4 μ m most preferably is preferably 0.1～0.25 μ m.If the average grain diameter of acrylic polymer particle A and acrylic polymer particle B is above-mentioned scope, the porous film strength that then obtains and flexibility become good.
Be scattered in graininess under the situation of decentralized medium at acrylic polymer particle A and acrylic polymer particle B, the solid component concentration of dispersion liquid is generally 15～70 quality %, preferred 20～65 quality %, further preferred 30～60 quality %.If solid component concentration is this scope, the operation when then making the perforated membrane slurry is good.
The glass transition temperature (Tg) that is used for acrylic polymer particle A of the present invention and B is preferably-50～25 ℃, more preferably-45～15 ℃, is preferably-40～5 ℃ especially.Tg by acrylic polymer particle A and acrylic polymer particle B is above-mentioned scope, and perforated membrane of the present invention has excellent intensity and flexibility, therefore, can improve the output characteristic of the secondary cell that has used this perforated membrane.In addition, the glass transition temperature of acrylic polymer particle A and acrylic polymer particle B can be adjusted by making up various monomers.
The manufacture method that is used for acrylic polymer particle A of the present invention and acrylic polymer particle B is not particularly limited, and also can use the arbitrary method in solution polymerization process, suspension polymerization, mass polymerization, the emulsion polymerization etc.As polymerization reaction, also can use the arbitrary reaction in ionic polymerization, radical polymerization, the active free radical polymerization etc.As the polymerization initiator that is used for polymerization; can enumerate for example lauroyl peroxide, diisopropyl peroxydicarbonate, two-2-ethylhexyl peroxy dicarbonate, the peroxidating neopentanoic acid tert-butyl ester, 3; 3; organic peroxide, α such as 5-trimethyl acetyl base peroxide, α '-azo-compound or ammonium persulfate, potassium peroxydisulfates etc. such as azodiisobutyronitrile.
Be used for acrylic polymer particle A of the present invention and acrylic polymer particle B preferably in its manufacturing process, remove operation and obtain through removing granular metallic particle shape metal contained among polymer beads dispersion liquid A and the polymer beads dispersion liquid B.Content by making granular metal composition contained among polymer beads dispersion liquid A and the polymer beads dispersion liquid B is below the 10ppm, can prevent between the polymer in the perforated membrane slurry through the time metal ion crosslinked, prevent that viscosity from rising.And then the worry that the self discharge that the dissolving during for the internal short-circuit of secondary cell or charging/separate out causes increases is less, and the cycle characteristics of battery and fail safe improve.
The method of removing granular metal ingredient from polymer beads dispersion liquid A and polymer beads dispersion liquid B that above-mentioned granular metal is removed in the operation is not particularly limited, and for example can enumerate: the method for removing by the filtration that utilizes filter, the method for removing by vibrating screen, the method for removing by centrifugation, the method for removing by magnetic force etc.Wherein, be metal ingredient owing to remove object, therefore, preferably remove by magnetic force.As the method for removing by magnetic force, as long as for the method that can remove metal ingredient just is not particularly limited, if consider productivity ratio and remove efficient, then preferably undertaken by configuration magnetic filter in the manufacturing line of acrylic polymer particle A and acrylic polymer particle B.
The manufacture method that is used for adhesive of the present invention is not particularly limited, can be by mixing above-mentioned polymer beads dispersion liquid A and polymer beads dispersion liquid B makes.Mixing arrangement be as long as for the device that polymer beads dispersion liquid A and polymer beads dispersion liquid B are mixed equably just is not particularly limited, for example can enumerate: used stirring-type, oscillatory type, and the method for rotary etc. mixing arrangement.In addition, can enumerate: the method for having used homogenizer, ball mill, sand mill, roller mill, planetary stirring machine and planetary mixing roll etc. to disperse kneading device.
The ratio that contains of acrylic polymer particle A in the adhesive is preferably 30～75 quality %, 33～66 quality % more preferably, and the ratio that contains of the acrylic polymer particle B in the adhesive is preferably 25～70 quality %, more preferably 33～66 quality %.If the acrylic polymer particle A in the adhesive and the ratio that contains of acrylic polymer particle B are above-mentioned scope, then cohesive force is good, and in addition, adhesive can tackify and disperse, and therefore, the flatness of perforated membrane is also excellent.
Sulfonic group among the acrylic polymer particle A in the adhesive is preferably 0.2～3 with respect to the weight ratio (sulfonic group/epoxy radicals) of the epoxy radicals among the acrylic polymer particle B, and more preferably 0.3～3, be preferably 0.3～2 especially.If the sulfonic group in the adhesive is above-mentioned scope with respect 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 that obtains improves.
The average grain diameter of adhesive is preferably 0.05～0.5 μ m, and more preferably 0.07～0.4 μ m is preferably 0.10～0.25 μ m especially.Average grain diameter can be by obtaining with the determination of laser diffraction particle size distribution.Be made as above-mentioned scope by the average grain diameter with adhesive, become well with the caking property of non-conductive particle, therefore, the flexibility of the secondary cell perforated membrane that obtains improves, and can prevent that non-conductive particle breaks away from (powder falls) from the secondary cell perforated membrane.Its result has used the secondary cell of this secondary cell perforated membrane to show excellent security and cycle characteristics.
With respect to all solids composition 100 quality % of perforated membrane slurry, the ratio that contains of adhesive is preferably 0.5～20 quality %, and more preferably 5～20 quality % are preferably 5～15 quality % especially.Be above-mentioned scope by making the ratio that contains with respect to the adhesive of all solids composition 100 quality % of perforated membrane slurry, can keep the cohesive force between the non-conductive particle well, improve the flexibility of perforated membrane.In addition, can improve the cycle characteristics of the secondary cell that obtains.
(solvent)
As the solvent that is used for the perforated membrane slurry, also can make in water and the organic solvent arbitrarily.As organic solvent, can enumerate: annular aliphatic hydro carbons such as pentamethylene, cyclohexane; Toluene, dimethylbenzene, ethylo benzene etc. are aromatic hydrocarbon based; Ketones such as acetone, ethyl methyl ketone, diisopropyl ketone, cyclohexanone, hexahydrotoluene, ethyl cyclohexane; Chlorine such as carrene, chloroform, carbon tetrachloride are aliphatic hydrocarbon; Ester classes such as ethyl acetate, butyl acetate, gamma-butyrolacton, 6-caprolactone; Nitrile such as acetonitrile, propionitrile (ア シ ロ ニ ト リ Le); Ethers such as oxolane, ethylene glycol diethyl ether: alcohols such as methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycol monoethyl ether; N-methyl pyrrolidone, N, amide-types such as dinethylformamide.
These solvents can use separately, also they can be mixed to make mixed solvent more than 2 kinds and use.Wherein, particularly the excellent dispersion of non-conductive particle, boiling point is low and volatility is high solvent can be removed under short time and low temperature, so preferred.Particularly, preferred acetone, toluene, cyclohexanone, pentamethylene, oxolane, cyclohexane, dimethylbenzene, water or N-methyl pyrrolidone or their mixed solvent.
(composition arbitrarily)
Except mentioned component (non-conductive particle, adhesive and solvent), can further contain composition arbitrarily in the perforated membrane slurry.As this composition arbitrarily, can enumerate: binding agent, tackifier, the defoamer beyond inorganic particle, dispersant, levelling agent, antioxidant, the above-mentioned adhesive and the compositions such as electrolysis additive with functions such as electrolyte decomposition inhibition.These however can just impact cell reaction and be not particularly limited.
As inorganic particle, can use for example various inorganic particles such as aluminium oxide, silica, magnesium oxide, titanium oxide, aluminium nitride, calcirm-fluoride, barium fluoride, talcum, montmorillonite.Not spherical special-shaped particle especially preferably.With respect to all solids composition 100 quality % of perforated membrane slurry, the ratio that contains of inorganic particle is below the 20 quality %, more preferably below the 10 quality %.If the ratio that contains of inorganic particle is this scope, then can obtain intensity by force and the good perforated membrane of permeability of lithium ion.
As dispersant, but illustration anionic property compound, cationic compound, nonionic compound, macromolecular compound.Dispersant can be selected according to the non-conductive particle that uses.With respect to all solids composition 100 quality % of perforated membrane slurry, dispersant contain the scope that ratio does not preferably impact battery behavior, particularly be below the 10 quality %.If the ratio that contains of dispersant is this scope, then the screening characteristics of perforated membrane slurry of the present invention is good, can obtain uniform perforated membrane.
As levelling agent, can enumerate: alkyl is that surfactant, silicon-type surfactant, fluorine are that surfactant, metal are surfactants such as surfactant.With respect to all solids composition 100 quality % of perforated membrane slurry, surfactant contain the scope that ratio does not preferably impact battery behavior, particularly be below the 10 quality %.By mixing above-mentioned surfactant, repel (は じ I) in the time of can preventing from being coated on perforated membrane slurry of the present invention on the basis material of regulation, 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.The polymer-type phenolic compound is the polymer that has the phenol structure in molecule, and can preferably to use weight average molecular weight be 200～1000, be preferably 600～700 polymer-type phenolic compound.With respect to all solids composition 100 quality % of perforated membrane slurry, antioxidant contain the scope that ratio does not preferably impact battery behavior, particularly be below the 10 quality %.If the ratio that contains of antioxidant is this scope, then the cycle life excellence of battery.
Binding agent as beyond the above-mentioned adhesive can use employed polytetrafluoroethylene (PTFE) in the binding agent for electrode described later, Kynoar (PVDF), polyacrylic acid derivative, polyacrylonitrile derivative, soft polymer etc.With respect to all solids composition 100 quality % of perforated membrane slurry, the ratio that contains of the binding agent beyond the above-mentioned adhesive is below the 10 quality %.If the ratio that contains of binding agent is this scope, then the adaptation of perforated membrane of the present invention and electrode active material layer described later, organic dividing plate is good.
As tackifier, can enumerate cellulose-based polymer and these ammonium salt and alkali metal salts such as carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose; (modification) poly-(methyl) acrylic acid and these ammonium salt and alkali metal salt; Copolymer, maleic anhydride or the maleic acid of (modification) polyvinyl alcohol, acrylic acid or acrylates and vinyl alcohol or the polyvinyl alcohols such as copolymer of 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.With respect to all solids composition 100 quality % of perforated membrane slurry, tackifier contain the scope that ratio does not preferably impact battery behavior, particularly be below the 10 quality %.If the ratio that contains of tackifier is this scope, 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) is poly-" refers to " unmodified poly-" or " modification is poly-", and " (methyl) acrylic acid " refers to " acrylic acid " or " methacrylic acid ".
As defoamer, use metallic soap class, polysiloxane-based, polyethers, higher alcohols, perfluoroalkyl class etc.With respect to all solids composition 100 quality % of perforated membrane slurry, defoamer contain the scope that ratio does not preferably impact battery behavior, particularly be below the 10 quality %.By mixing defoamer, can shorten the froth breaking operation of adhesive.
Electrolysis additive can use in electrode slurry described later and electrolyte in employed vinylene carbonate etc.With respect to all solids composition 100 quality % of perforated membrane slurry, electrolysis additive contain the scope that ratio does not preferably impact battery behavior, particularly be below the 10 quality %.By the mixed electrolytic solution additive, the cycle life excellence of battery.
In addition, can enumerate: nanoparticles such as aerosil and gaseous oxidation aluminium.By mixing above-mentioned nanoparticle, can control the thixotropy of perforated membrane slurry, and then, can improve the levelability of the perforated membrane that obtains thus.
With respect to all solids composition 100 quality % of perforated membrane slurry, the summation that contains ratio of above-mentioned composition arbitrarily is preferably below the 40 quality %, more preferably below the 20 quality %.But, above-mentioned non-conductive particle, adhesive and arbitrarily the summation of composition (wherein, not comprising inorganic particle, binding agent) be lower than under the situation of 100 quality %, suitable increment can obtain composition as the ratio that contains of the binding agent of composition arbitrarily.
The solid component concentration of perforated membrane slurry needs only to the degree of the coating that can carry out this slurry, dipping and has mobile viscosity and just is not particularly limited, and generally speaking is about 10～50 quality %.
Composition beyond the solid constituent is for the composition by dry operation volatilization, except above-mentioned solvent, for example also is included in the preparation of non-conductive particle and adhesive and dissolves or disperse their medium when adding.
The manufacture method of secondary cell perforated membrane slurry is not particularly limited, and can assign to make by the one-tenth arbitrarily that mixes above-mentioned non-conductive particle, adhesive, solvent and add as required.In the present invention, by using and mixing mentioned component (non-conductive particle, adhesive, solvent and the composition arbitrarily that adds 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 manufacturing that is used for above-mentioned adhesive.Wherein, preferred especially use can apply the contour dispersal device of ball mill, roller mill, Filmix that high dispersive is sheared.
The viscosity of perforated membrane slurry is considered from the viewpoint of even screening characteristics, slurry ageing stability, is preferably 10～10,000mPas, more preferably 50～500mPas.Value when above-mentioned viscosity is measured under 25 ℃, the condition of revolution 60rpm for using Brookfield viscometer.
(2) secondary cell perforated membrane
Secondary cell perforated membrane of the present invention (below, be expressed as " perforated membrane " sometimes.) be above-mentioned secondary cell perforated membrane slurry to be formed membranaceous and carries out drying form.
Perforated membrane is stacked on organic dividing plate or electrode and uses or itself use as organic dividing plate.
The manufacture method of＜secondary cell perforated membrane 〉
As the method for making perforated membrane of the present invention, can enumerate: (I) will contain above-mentioned non-conductive particle, adhesive, solvent and arbitrarily the perforated membrane slurry of composition be coated on the basis material (anodal, negative pole or organic dividing plate) of regulation, carry out dry method then; (II) will contain above-mentioned non-conductive particle, adhesive, solvent and after the perforated membrane slurry of composition impregnated in basis material (anodal, negative pole or organic dividing plate) arbitrarily, it will be carried out dry method; (III) will contain above-mentioned non-conductive particle, adhesive, solvent and arbitrarily the perforated membrane slurry of composition be coated on and carry out film forming on the stripping film, with the perforated membrane transfer printing that the obtains method on the basis material of regulation (anodal, negative pole or organic dividing plate).Wherein, (I) perforated membrane slurry is coated on the basis material (positive pole, negative pole or organic dividing plate), carries out the thickness that dry method is controlled perforated membrane easily then, so most preferably.
Perforated membrane of the present invention is by the method manufacturing of above-mentioned (I)～(III), below, its detailed manufacture method is described.
In the method for (I), the basis material (anodal, negative pole or organic dividing plate) that the perforated membrane slurry is coated on regulation is gone up and is carried out drying, makes perforated membrane of the present invention thus.
The method that this slurry is coated on the basis material is not particularly limited, and for example can enumerate: methods such as scraper rubbing method, reverse roll method, direct roller method, intagliotype, extrusion, spread coating.Wherein, consider preferred intagliotype from the aspect that can obtain uniform perforated membrane.
As drying means, can enumerate: utilize for example seasoning of the irradiations such as drying, vacuumize, utilization (far) infrared ray or electron beam of warm wind, hot blast, low wet wind.Baking temperature can change according to the solvent types of using.For complete desolventizing, for example under the situation of the low solvent of volatility such as use N-methyl pyrrolidone, preferably the drying machine with blast type carries out drying under the high temperature more than 120 ℃.On the contrary, under the situation of using the high solvent of volatility, also can under the low temperature below 100 ℃, carry out drying.When organic dividing plate described later forms perforated membrane, carry out drying owing to need not cause the contraction ground of organic dividing plate, therefore, the preferred drying under the low temperature below 100 ℃.
In the method for (II), the perforated membrane slurry be impregnated in basis material (positive pole, negative pole or organic dividing plate) and carries out drying, make perforated membrane of the present invention thus.The method that this slurry be impregnated in basis material is not particularly limited, and for example can flood by carrying out dip coated with dip coater etc.
As drying means, can enumerate the identical method of drying means in the method with above-mentioned (I).
In the method for (III), be coated on the perforated membrane slurry on the stripping film and carry out film forming, make the perforated membrane that is formed on the stripping film.Then, with the perforated membrane transfer printing that obtains on basis material (anodal, negative pole or organic dividing plate).
As coating process, can enumerate the identical method of coating process in the method with above-mentioned (I).Printing transferring method is not particularly limited.
(I)～(III) perforated membrane that obtains in the method 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 then as required.But at this moment, if excessively carry out pressurized treatments, then the voidage of perforated membrane is impaired sometimes, therefore, and suitable controlled pressure and pressing time.
The thickness of perforated membrane is not particularly limited, can be according to purposes or the suitable setting of application of perforated membrane, if it is thin excessively, then can't form uniform film, on the contrary, if blocked up, then the capacity (capacity) of the unit volume (weight) in the battery reduces, therefore, preferred 0.5～50 μ m, more preferably 0.5～10 μ m.
Perforated membrane of the present invention especially is preferably used as diaphragm or the dividing plate of electrode active material layer described later at the surface filming of basis material (positive pole, negative pole or organic dividing plate).Perforated membrane of the present invention can the arbitrary surfaces in positive pole, negative pole or organic dividing plate of secondary cell on film forming, also can anodal, 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, because that lithium rechargeable battery requires the raising of fail safe and perforated membrane to import effect most is the highest, thus preferred, therefore, below the situation that is used for lithium rechargeable battery is described.
Electrode for secondary battery of the present invention contains: collector body, be attached to this collector body and form and contain the electrode active material layer of electrode active material and binding agent and be stacked in the lip-deep above-mentioned secondary cell perforated membrane of this electrode active material layer.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 forms at the above-mentioned secondary cell perforated membrane of the surperficial superimposed layer of electrode active material layer in the surface attachment of collector body.
(electrode active material)
Employed electrode active material in the electrode for lithium ion secondary battery so long as can reversibly insert the active material of emitting lithium ion and get final product by apply electromotive force in electrolyte, and inorganic compound or organic compound all can use.
The electrode active material that lithium ion secondary battery positive electrode is used (positive active material) roughly divides for the active material that is made of inorganic compound and the active material that is made of organic compound.As the positive active material that is constituted by inorganic compound, can enumerate: the composite oxides of transition metal oxide, lithium and transition metal, transient metal sulfide etc.As above-mentioned transition metal, use Fe, Co, Ni, Mn etc.As the concrete example of employed inorganic compound in the 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 carry out the compound that element replaces for part.As the positive active material that is constituted by organic compound, for example also can use electroconductive polymers such as polyacetylene, polyparaphenylene.The ferrous oxide of conductivity deficiency also can be used as the electrode active material that covers with material with carbon element and uses by there is carbon source material when reduction is fired.In addition, these compounds can carry out the compound that the element replacement forms for part.
The positive active material that lithium rechargeable battery is used can be above-mentioned inorganic compound and the mixture of organic compound.The constitutive requirements arbitrarily that the particle diameter of positive active material can be taken into account battery suit to select, but consider from the viewpoint that battery behaviors such as multiplying power property, cycle characteristics improve, and 50% volume accumulation particle diameter is generally 0.1～50 μ m, is preferably 1～20 μ m.If 50% volume accumulation particle diameter be this scope, can obtain the big secondary cell of charge/discharge capacity, and the processing ease when manufacturing electrode slurry and electrode.50% volume accumulation particle diameter can be by obtaining with the determination of laser diffraction particle size distribution.
As the electrode active material (negative electrode active material) that lithium ion secondary battery negative pole is used, for example can enumerate: electroconductive polymer compounds such as carbonaceous materials such as amorphous carbon, graphite, native graphite, carbonaceous mesophase spherules, pitch-based carbon fiber, poly-acene etc.In addition, as negative electrode active material, use oxide and the sulfate of metal such as silicon, tin, zinc, manganese, iron, nickel and their alloy, above-mentioned metal or alloy.In addition, can use lithium alloys such as lithium metal, Li-Al, Li-Bi-Cd, Li-Sn-Cd, lithium transition-metal nitride, silicone etc.Electrode active material also can use by the mechanically modifying method in surface attachment conduction give the active material that material forms.Other the constitutive requirements that the particle diameter of negative electrode active material can be taken into account battery suit to select, consider that from the viewpoint of the raising of battery behaviors such as initial stage efficient, multiplying power property, cycle characteristics 50% volume accumulation particle diameter is generally 1～50 μ m, is preferably 15～30 μ m.
(binding agent for electrode)
In the present invention, electrode active material layer except electrode active material, contain binding agent (below, be designated as " binding agent for electrode " sometimes.)。By containing binding agent for electrode, the caking property of the electrode active material layer in the electrode improves, electrode roll around the time etc. on the operation intensity of force with respect to this machinery rise, in addition, electrode active material layer in the electrode becomes and is difficult for breaking away from, therefore, the danger that breaks away from short circuit that thing causes etc. diminishes.
As binding agent for electrode, can use various resinous principles.For example can use polyethylene, polytetrafluoroethylene (PTFE), Kynoar (PVDF), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivative, polyacrylonitrile derivative etc.These may be used singly or in combination of two or more.In addition, also can will be used for the adhesive of perforated membrane of the present invention as binding agent for electrode.
And then, below illustrative soft polymer also can be used as binding agent for electrode.
Can enumerate the acrylic acid series soft polymer: the homopolymers of butyl polyacrylate, polybutyl methacrylate, polymethylacrylic acid hydroxy methacrylate, polyacrylamide, polyacrylonitrile, n butyl acrylate styrene, butyl acrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile-acrylic or methacrylic acid derivatives such as glycidyl methacrylate copolymer or and can with the copolymer of the monomer of its copolymerization;
Isobutenes such as polyisobutene, butyl rubber, isobutylene-styrene copolymer are soft polymer;
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;
Siliceous soft polymers such as dimethyl polysiloxane, diphenyl polysiloxanes, dihydroxy polysiloxanes;
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-styrol copolymer;
Ethene base system soft polymers such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinylacetate-styrol copolymer;
Epoxies such as poly(ethylene oxide), PPOX, epichlorohydrin rubber are soft polymer;
Fluorine-containing soft polymers such as vinylidene fluoride rubber, tetrafluoroethylene-acrylic rubber;
Other soft polymer etc. such as natural rubber, polypeptide, protein, polyester based thermoplastic elastomer, vinyl chloride thermoplastic elastomer (TPE), polyamide-based thermoplastic elastomer (TPE).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 the electrode active material layer is 0.1～5 mass parts with respect to electrode active material 100 mass parts preferably, and more preferably 0.2～4 mass parts is preferably 0.5～3 mass parts especially.Be above-mentioned scope by the binding agent for electrode amount in the electrode active material layer, can not hinder cell reaction ground and suppress active material and break away from from electrode.
In order to make electrode, binding agent for electrode is prepared with the form of solution or dispersion liquid.The viscosity of this moment is generally the scope of 1～300,000mPas, is preferably 50～10,000mPas.Value when above-mentioned viscosity is measured under 25 ℃, the condition of revolution 60rpm for using Brookfield viscometer.
(additive arbitrarily)
In the present invention, electrode active material layer also can contain conductivity and give additive arbitrarily such as material and reinforcing material except above-mentioned electrode active material and binding agent for electrode.Give material as conduction, can enumerate; 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 carbon dusts such as graphite, various metals and paper tinsel etc.As reinforcing material, can use various inorganic organically spherical, tabular, the bar-shaped or fibrous fillers that reaches.By using conductivity to give material, can improve electrode active material electrically contacting each other, be used for can improving discharge-rate characteristic (レ ー ト characteristic under the situation of lithium rechargeable battery).The use amount that conductivity is given material and reinforcing material is generally 0～20 mass parts with respect to electrode active material 100 mass parts, is preferably 1～10 mass parts.In addition, in electrode active material layer, also can contain isothiazoline based compound and complex compound compound.
Electrode active material layer can make the slurry that contains electrode active material, binding agent for electrode and solvent (below, be sometimes referred to as " electrode slurry ".) be attached on the collector body and form.
As solvent, so long as lysis electrodes is with binding agent or make it be dispersed into granular solvent to get final product the solvent that preferably dissolves.If use lysis electrodes with the solvent of binding agent, then be adsorbed in electrode active material by binding agent for electrode and reach the surface of additive arbitrarily, the decentralized stabilization of electrode active material etc.
As the solvent that is used for electrode slurry, can make in water and the organic solvent arbitrarily.As organic solvent, can enumerate: annular aliphatic hydro carbons such as pentamethylene, cyclohexane; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; Ketone such as ethyl methyl ketone, cyclohexanone; Ester classes such as ethyl acetate, butyl acetate, gamma-butyrolacton, 6-caprolactone; Nitrile such as acetonitrile, propionitrile; Ethers such as oxolane, ethylene glycol diethyl ether; Alcohols such as methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycol monoethyl ether; N-methyl pyrrolidone, N, amide-types such as dinethylformamide.These solvents can separately or mix more than 2 kinds, and the viewpoint on rate of drying and environment is considered the suitable use of selecting.
Can further contain the additive that tackifier etc. show various functions in the electrode slurry.As tackifier, use the polymer that dissolves in solvent that is used for electrode slurry.Particularly, can use illustrative tackifier in the perforated membrane slurry of the present invention.The use amount of tackifier is 0.5～1.5 mass parts with respect to electrode active material 100 mass parts preferably.If the use amount of tackifier is above-mentioned scope, then the screening characteristics of electrode slurry reaches with the adaptation of collector body good.
And then, in electrode slurry, except mentioned component, for stability and the life-span of improving battery, can use trifluoro propylene carbonate, vinylene carbonate, catechol carbonic ester, 1,6-dioxo spiro [4,4] nonane-2,7-diketone, 12-crown-4-ether etc.In addition, these can contain in electrolyte described later and use.
According to the kind of electrode active material and binding agent for electrode etc., thereby the amount of adjusting the solvent in the electrode slurry forms the viscosity that is suitable for applying.Particularly, preferred adjust make in electrode slurry electrode active material, binding agent for electrode and conductivity give material etc. arbitrarily the concentration of the solid constituent that amounts to of additive be 30～90 quality %, the amount of 40～80 quality % and use more preferably.
Use mixer with electrode active material, binding agent for electrode, the conductivity of adding as required give material etc. arbitrarily additive and solvent mix, thereby obtain electrode slurry.Mixing also can be supplied in each above-mentioned composition in the lump mixer and mix.Give under material and the situation of tackifier as the constituent of electrode slurry in use electrode active material, binding agent for electrode, conductivity, because it is microgranular giving with conductivity that material and tackifier mix and make conductivity give dispersion of materials in solvent, then, interpolation binding agent for electrode, electrode active material further mix the dispersiveness that makes slurry and improve, and be therefore preferred.As mixer; can use ball mill, sand mill, pigment dispersion machine, mixing and kneading machine, ultrasonic dispersing machine, homogenizer, planetary stirring machine, Hobart's mixer etc.; if use ball mill, then can suppress the cohesion that conductivity is given material and electrode active material, so preferred.
The granularity of electrode slurry is preferably below the 35 μ m, more preferably below the 25 μ m.If the granularity of slurry is above-mentioned scope, then can obtains conductivity and give the dispersed height of material and the electrode of homogeneous.
(collector body)
As long as collector body is considered from having stable on heating viewpoint, for example metal materials such as preferred iron, copper, aluminium, nickel, stainless steel, titanium, tantalum, gold, platinum for the material that has conductivity and have an electrochemistry durability just is not particularly limited.Wherein, as the positive pole usefulness of lithium rechargeable battery, preferred especially aluminium, as the negative pole usefulness of lithium rechargeable battery, special preferably copper.The shape of collector body is not particularly limited, the collector body of the sheet about preferred thickness 0.001～0.5mm.Collector body preferably carries out the asperities processing in advance and uses in order to improve the adhesive strength of electrode active material layer.As the asperities method, can enumerate: mechanical polishing method, electrobrightening method, chemical polishing etc.In mechanical polishing method, the used set sand paper of polishing agent particle, grinding stone, diamond dust, possesses the line brush of steel wire etc. etc.In addition, for adhesive strength and the conductivity that improves electrode active material layer, can form the intermediate layer on the 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 on the one side at least of above-mentioned collector body, preferred two sides.For example be coated on above-mentioned electrode slurry on the collector body and carry out drying, carrying out heat treated more than 1 hour more than 120 ℃ then, form electrode active material layer.The method that electrode slurry is coated on the collector body is not particularly limited.For example can enumerate: methods such as scraper rubbing method, infusion process, reverse roll method, direct roller method, intagliotype, extrusion, spread coating.As drying means, can enumerate: utilize for example seasoning of the irradiations such as drying, vacuumize, utilization (far) infrared ray or electron beam of warm wind, hot blast, low wet wind.
Then, preferably use moulding press or roll squeezer, reduce the voidage of electrode active material layer by pressurized treatments.The preferred range of voidage is 5～15%, more preferably 7～13%.If voidage is too high, then charge efficiency and discharging efficiency variation.Under the low excessively situation of voidage, produce and to be difficult to obtain high volume capacity or electrode active material layer and to peel off easily and be easy to generate the such problem of unfavorable condition.And then, under the situation of the polymer that uses curing property, preferably be cured.
For the thickness of electrode active material layer, anodal, negative pole all is generally 5～300 μ m, is preferably 10～250 μ m.
Electrode for secondary battery of the present invention is made by the electrode active material layer surface superimposed layer secondary cell perforated membrane of the present invention at the collector body of the electrode active material layer of the promising stratiform of bonding.
Laminating method is not particularly limited, and can enumerate: the method for (I)～(III) that illustrates in the manufacture method of above-mentioned perforated membrane.
(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 above-mentioned secondary cell perforated membrane of organic dividing plate superimposed layer.
(organic dividing plate)
Organic dividing plate of using as lithium rechargeable battery uses vistanex such as polyethylene, polypropylene or contains the known dividing plates such as dividing plate that aromatic polyamide resin forms.
As being used for organic dividing plate of the present invention, use does not have electronic conductivity and has ionic conductivity, the fine multiple aperture plasma membrane of the patience height of organic solvent and aperture can be enumerated by for example polyolefin (polyethylene, polypropylene, polybutene, polyvinyl chloride), and resins such as these mixture or copolymer constitute micro-porous film, by PETG, poly-cycloolefin, polyether sulfone, polyamide, polyimides, polyimide amide, Nomex, poly-cycloolefin, nylon, the micro-porous film that resins such as polytetrafluoroethylene constitute or the fibrage of polyolefin form, or its nonwoven fabrics, the aggregate of insulating properties material grains etc.Wherein, from the screening characteristics excellence of perforated membrane slurry of the present invention, thickness that can attenuate dividing plate integral body, the aspect that improves the active material ratio in the battery and improve the capacity of unit volume consider, preferably the micro-porous film that is made of the resin of polyolefin.
The thickness of organic dividing plate is generally 0.5～40 μ m, is preferably 1～30 μ m, more preferably 1～20 μ m.If this scope, the then resistance decreasing brought of the organic dividing plate in the battery.In addition, the operability of perforated membrane slurry coating of the present invention when organic dividing plate is good.
In the present invention, as the resin as the polyolefin of the material of organic dividing plate, can enumerate: homopolymers, copolymer and their mixture of polyethylene, polypropylene etc.As polyethylene, can enumerate low-density, middle density, highdensity polyethylene, consider preferred highdensity polyethylene from the viewpoint of puncture intensity and mechanical strength.In addition, these polyethylene are considered from the purpose of giving flexibility, also can be mixed more than 2 kinds.Be used for these poly polymerization catalysts and also be not particularly limited, can enumerate: Z-N series catalysts, Philips series catalysts and metallocene series catalysts etc.Consider that from the viewpoint that has both mechanical strength and high-permeability poly viscosity average molecular weigh is preferred 100,000～1,200 ten thousand, more preferably 200,000～3,000,000.As polypropylene, can enumerate: homopolymers, random copolymer, block copolymer, can mix one or two or more kinds and use.In addition, polymerization catalyst also is not particularly limited, and can enumerate: Z-N series catalysts and metallocene series catalysts etc.In addition, stereospecificity also is not particularly limited, and can use isotaxy, syndiotaxy and atactic, but considers from the aspect of cheapness, preferably uses isotactic polypropylene.And then, also can be in the scope of not damaging effect of the present invention in polyolefin an amount of additives such as Polyolefin and antioxidant beyond polyethylene or the polypropylene, nucleator that add.
Method as organic dividing plate of making polyolefin, can use public method, for example can from following method, select: with polypropylene, polyethylene melt extrude make film after, make its annealing at low temperatures, make the crystallized domains growth, under this state, stretch, non-crystalline areas is stretched, form the dry method of micro-porous film thus; After hydrocarbon solvent and other low molecular material and polypropylene, polyethylene mixed, form film, then, compile and begin to form the film of island phase at solvent in amorphous phase and low molecule, by using other solvent that volatilizees easily to remove this solvent, low molecule, form the wet method of micro-porous film etc. thus.Wherein, consider the preferred dry method from the aspect that obtains bigger space for the purpose that reduces resistance, easily.
For the purpose of controlling intensity and hardness, percent thermal shrinkage, be used for organic dividing plate of the present invention and also can contain filler and compound arbitrarily.In addition, under the situation of lamination perforated membrane of the present invention, improve or reduce the purpose that makes the impregnation raising of liquid with respect to the surface tension of electrolyte for the adaptation that makes organic dividing plate and perforated membrane, also can be in advance be covered with low molecular compound or macromolecular compound and handle or carry out plasmas such as electromagnetic wire processings, corona discharge-plasma gas processing such as ultraviolet ray.
Particularly high and obtain easily considering with the aspect of the adaptation of above-mentioned perforated membrane from the impregnation of electrolyte, preferably with the macromolecular compound that contains carboxylic acid group, hydroxyl and the sulfonic group isopolarity group processing that is covered.
Secondary battery separator of the present invention is by making 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 for explanation (I)～(III) 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, forms at the above-mentioned perforated membrane of any superimposed layer of anodal, negative pole and organic dividing plate.
(electrolyte)
As electrolyte, use and in organic solvent, dissolved the organic electrolyte that supporting electrolyte forms.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, the preferred LiPF that easily is dissolved in solvent and shows higher degree of dissociation 6, LiClO 4, CF 3SO 3Li.These also can be used in combination more than two kinds.Owing to more use the high supporting electrolyte lithium ion conduction degree of degree of dissociation more high, therefore, can regulate the lithium ion conduction degree according to the kind of supporting electrolyte.
As the organic solvent that is used for electrolyte, as long as for the solvent that can dissolve supporting electrolyte just is not particularly limited, can preferably use dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), methyl ethyl carbonate carbonates such as (MEC); Ester such as gamma-butyrolacton, methyl formate class; Ethers such as 1,2-dimethoxy-ethane, oxolane; Sulfur-containing compound such as sulfolane, dimethyl sulfoxide (DMSO) class.In addition, also can use the mixed liquor of these solvents.Wherein, because carbonates dielectric constant height, stable voltage belt field width, so preferred.Because the viscosity of the solvent that uses is more low, it is more high that the lithium ion conduction degree becomes, and therefore, can regulate the lithium ion conduction degree according to solvent types.
The concentration of the supporting electrolyte in the electrolyte is generally 1～30 quality %, is preferably 5～20 quality %.In addition, according to the kind of supporting electrolyte, use with the concentration of 0.5～2.5 mole/L usually.The concentration of supporting electrolyte is crossed the low or too high tendency that all exists ionic conductance to reduce.Because the concentration of the electrolyte that uses the more swellbility of low polymer particle becomes more big, therefore, can be according to the concentration adjustment lithium ion conduction degree of electrolyte.
As the concrete manufacture method of secondary cell, can enumerate: positive pole and negative pole are carried out via organic dividing plate superimposed, with its according to cell shapes curl, bending etc. puts into battery case, injects electrolyte and method for sealing to battery case.Perforated membrane of the present invention be stacked in positive pole, negative pole, and organic dividing plate arbitrarily on.The method that perforated membrane of the present invention is stacked on positive pole, negative pole and organic dividing plate is as described in above-mentioned (I) or method (II).In addition, as described in the method for above-mentioned (III), also can only perforated membrane be stacked on positive pole, negative pole or organic dividing plate independently.Also can put into overcurrent such as expansion alloy, fuse, PTC element as required and prevent that element, lead plate from waiting to prevent that the pressure of inside battery from rising, discharging and recharging excessively.The shape of battery can be Any shape such as Coin shape, coin shape, sheet 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 the electrode active material layer surface, even organic dividing plate causes the contraction that thermal conductance causes, can not cause the short circuit between positive pole, negative pole yet, guarantee higher fail safe.In addition, by perforated membrane of the present invention is stacked on the electrode active material layer surface, even without organic dividing plate, perforated membrane also can be brought into play the function as dividing plate, can be with low-cost production's secondary cell.In addition, even under the situation of using organic dividing plate, also can not fill up formed hole on the baffle surface, 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.Illustrated that the part in the present embodiment and % then are quality criteria unless otherwise specified.In embodiment and comparative example, various rerum naturas are following to be estimated.
The heat resisting temperature of＜non-conductive particle (T10 value) 〉
Under blanket of nitrogen, heat for 10 ℃/minute from 30 ℃ with programming rate with thermobalance, the loss of weight ratio of obtaining non-conductive particle reach the temperature of 10 quality % [℃], as heat resisting temperature.
The average grain diameter of＜non-conductive particle 〉
From the photo of taking with 25000 times multiplying power with electron microscope, at random select 100 non-conductive particles, with the longest edge of its particle picture be made as a, when will minor face being made as b, (a+b)/2 are made as particle diameter, calculate average grain diameter [μ m] by 100 mean values.
The average circularity of＜non-conductive particle 〉
At random select 100 non-conductive particles from the photo of taking with 25000 times multiplying power with electron microscope, the girth that will have the circle of the projected area identical with its particle image is made as L 0, when the girth of particle image is made as L, with L 0/ L is made as circularity, calculates average circularity by 100 mean values.
＜non-conductive particle grain size distribution 〉
Non-conductive particle grain size distribution is made as the volume average particle size that obtains V, number average bead diameter is made as N after carrying out particle size determination with the laser diffraction of Beckman Co., Ltd. system refraction particle size distribution device (LS230), obtains with following formula.
Particle diameter 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 meter (MH-15M) that the thickness of the secondary cell perforated membrane that is cut into or electrode for secondary battery is used the Nikon of Co., Ltd. system is measured 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, estimate with following benchmark.
[mathematical expression 1]
The standard deviation of thickness σ = nΣ x 2 - ( Σx ) 2 n 2
Inequality=the σ of thickness/x * 100 (%)
At this, x represents the mean value of thickness, and n represents to measure number.
(metewand)
A: be lower than 2%
More than the B:2%～be lower than 3%
More than the C:3%～be lower than 10%
More than the 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) punching is become the circle of diameter 19mm, in nonionic surfactant (KAO. Corp. SA's system; Emulgen210P) dipping and air-dry in the 3 weight % methanol solutions.Impregnation electrolyte in this circular secondary battery separator is held on the SUS plate (diameter 15.5mm) of a pair of circle, is overlapped into (SUS plate)/(circular secondary battery separator)/(SUS plate) such structure.At this, electrolyte uses in the mixed solvent that ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed with EC:DEC=1:2 (volumetric ratios under 20 ℃) and dissolves LiPF with the concentration of 1 mol 6The solution that forms.It is enclosed 2032 type coin batteries.From this coin battery, get lead-in wire, put into the baking box of additional heat galvanic couple.Alternating current while the frequency that applies amplitude 10mV, 1kHz is warming up to 200 ℃ for 1.6 ℃/minute with programming rate, measures the cell resistance of this process, confirms the situation occurred of short circuit thus.In this test, resistance value rose owing to cut off when temperature rose, and was at least 1000 Ω/cm 2More than.Then, be reduced to 10 Ω/cm rapidly 2Following situation is made as short circuit and takes place.In addition, carry out this test 20 times, estimate with following benchmark.
(metewand)
A: short circuit takes place several 0
B: short circuit takes place several 1
C: short circuit takes place several 2～3
D: short circuit takes place several more than 4
The reliability test of＜electrode for secondary battery (electrode of band perforated membrane) 〉
Organic dividing plate (polypropylene of individual layer dividing plate processed, the porosity 55%, thickness 25 μ m) punching is become the circle of diameter 19mm, be immersed in nonionic surfactant (KAO. Corp. SA's system; Emulgen210P) also air-dry in the 3 weight % methanol solutions.On the other hand, electrode for secondary battery (electrode of the band perforated membrane) punching with determination object becomes 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 of circle, be overlapped into (SUS plate)/(circular organic dividing plate)/(circular electrode for secondary battery)/(SUS plate) such structure.Circular electrode for secondary battery is set, and to make the face of its perforated membrane side be organic bulkhead sides.At this, electrolyte uses in the mixed solvent that ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed with EC:DEC=1:2 (volumetric ratios under 20 ℃) and dissolves LiPF with the concentration of 1 mol 6The solution that forms.It is enclosed 2032 type coin batteries.From coin battery, get lead-in wire, put into the baking box of additional heat galvanic couple.Alternating current while the frequency that applies amplitude 10mV, 1kHz is warming up to 200 ℃ for 1.6 ℃/minute with programming rate, measures the cell resistance of this process, confirms the situation occurred of short circuit thus.In this test, resistance value rose owing to cut off when temperature rose, and was at least 1000 Ω/cm 2More than.Be reduced to 10 Ω/cm then rapidly 2Following situation is made as short circuit.In addition, carry out this test 20 times, estimate with following benchmark.
(metewand)
A: short circuit takes place several 0
B: short circuit takes place several 1～2
C: short circuit takes place several more than 3
The cycle characteristics of＜secondary cell 〉
Will be under 20 ℃ with the constant current charge of 0.2C to 4.3V, with the constant-current discharge of 0.2C to the operation of 3.0V as 1 circulation, the secondary cell (Coin-shaped battery) that obtains is repeated to discharge and recharge.With percentage calculate the 100th discharge capacity in the circulation with respect to the ratio of the discharge capacity in the 2nd circulation as charge, judge with following benchmark.This value is more big, and expression repeats to discharge and recharge the capacity that causes and reduces more few.
(metewand)
More than the A:97%
B:95% is above and be lower than 97%
C:90% is above and be lower than 95%
D:85% is above and be lower than 90%
E: be lower than 85%
The mealiness that falls of＜electrode for secondary battery (electrode of band perforated membrane) 〉
It is square that electrode for secondary battery (electrode of band perforated membrane) is cut into 5cm, puts into the vial of 500ml, vibrated 3 hours with 300rpm with oscillator.The quality of powder of will falling is considered as a, the quality of the electrode for secondary battery before will vibrating is considered as b, with the quality of the electrode before the lamination perforated membrane be considered as c, not the lamination perforated membrane only the quality of the powder that falls during the electrode vibration be considered as d, calculate the ratio X[quality % of powder with following formula], estimate with following benchmark.
X=(a-d)/(b-c-a) * 100[quality %]
(metewand)
A: be lower than 2 quality %
B:2 quality % is above and be lower than 5 quality %
More than the C:5 quality %
The mealiness that falls of＜secondary battery separator (organic dividing plate of band perforated membrane) 〉
It is square that secondary battery separator (organic dividing plate of band perforated membrane) is cut into 5cm, puts into the vial of 500ml, vibrated 3 hours with 300rpm with oscillator.With the quality of secondary battery separator before the vibration be considered as a, the quality of secondary battery separator after will vibrating is considered as b, calculate the ratio X[quality % of powder with following formula], estimate with following benchmark.
X=(a-b)/a * 100[quality %]
(metewand)
A: be lower than 1 quality %
B:1 quality % is above and be lower than 3 quality %
C:3 quality % is above and be lower than 5 quality %
D:5 quality % is above and be lower than 10 quality %
More than the E:10 quality %
The mensuration that contains ratio of the sulfonic group the in＜polymer beads and epoxy radicals 〉
If with the addition with sulfonic monomer [g] that adds when the polymerization of acrylic polymer particle A be considered as a, with molecular weight be considered as b, the molecular weight that the sulfonic group part is suitable is considered as c (81.07), the monomer total amount is considered as d, then the sulfonic ratio [quality %] that contains of (with respect to the monomer total amount) calculates by the mode of following formula among the acrylic polymer particle A.
The sulfonic ratio (A) that contains among the acrylic polymer particle A
=(a/b) * c/d * 100[quality %]
Equally, if with the addition [g] of the monomer with epoxy radicals that adds when the polymerization of acrylic polymer particle B be considered as e, with molecular weight be considered as f, the molecular weight that the epoxy radicals part is suitable is considered as g (43.05), the monomer total amount is considered as h, then the ratio [quality %] that contains of the epoxy radicals of (with respect to the monomer total amount) calculates by the mode of following formula among the acrylic polymer particle B.
Epoxy radicals among the acrylic polymer particle B contain ratio (B)
=(e/f) * g/h * 100[quality %]
Sulfonic group in the＜adhesive is with respect to the mensuration of the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals 〉
The solid constituent amount [g] of the acrylic polymer particle A that adds when slurry is made is considered as C, the solid constituent amount [g] of the acrylic polymer particle B of interpolation when slurry is made is considered as D.And then, the sulfonic sulfonic ratio (B) that contains that contains among ratio (A) and the acrylic polymer particle B among the acrylic polymer particle A that obtains in sulfonic group in the use polymer beads and the mensuration that contains ratio of epoxy radicals is by the weight ratio of following manner calculating sulfonic group/epoxy radicals.
Sulfonic group/epoxy radicals=(A * C)/(B * D) [weight ratio]
(embodiment 1)
The manufacturing of＜(1) seeding polymerization composition granule A 〉
In having the reactor of mixer, put into 100 parts of styrene, 1.0 parts of neopelexes, 100 parts of ion exchange waters, reach 0.5 part of potassium peroxydisulfate, 80 ℃ of following polymerizations 8 hours.Thus, obtain the aqueous dispersion of the seeding polymerization composition granule A of average grain diameter 60nm.
The manufacturing of＜(2) seeding polymerization composition granule B 〉
The aqueous dispersion of putting into the seeding polymerization composition granule A that operation (1) obtains in having the reactor of mixer is counted 100 parts of 2 parts, 0.2 part of neopelex, 0.5 part of potassium peroxydisulfate and ion exchange waters with solid constituent benchmark (being the weight basis of seeding polymerization composition granule A), mix, obtain mixture, be warming up to 80 ℃.On the other hand, 97 parts of benzene mixed ethene, 3 parts of methacrylic acids, 4 parts of uncle's lauryl mercaptans, 0.5 part of neopelex and ion exchange water are 100 parts in another container, the dispersion of preparation monomer mixture.The dispersion of this monomer mixture was added into continuously through 4 hours makes its polymerization in the said mixture.The temperature of the reaction system in the continuous interpolation process of the dispersion of monomer mixture remains 80 ℃, reacts.Continuous interpolation finishes the back, further continues reaction 3 hours down at 90 ℃.
Thus, obtain the aqueous dispersion of the seeding polymerization composition granule B of average grain diameter 200nm.
The manufacturing of the non-conductive particle in＜(3) 〉
Then, in having the reactor of mixer, put into the aqueous dispersion of the seeding polymerization composition granule B that operation (2) obtains in 10 parts of solid constituent benchmark (being seeding polymerization composition granule B weight basis), 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, 1 part of neopelex, peroxidating (2 ethyl hexanoic acid) tert-butyl ester (day oily corporate system as polymerization initiator, trade name: Perbutyl O) 5 parts and ion exchange water are 200 parts, stirred 12 hours down at 35 ℃, make seeding polymerization composition granule B absorb monomer mixture and polymerization initiator fully thus.Then, with it 90 ℃ of following polymerizations 4 hours.Then, import steam and remove unreacted monomer.
Thus, obtain the aqueous dispersion of the non-conductive particle of average grain diameter 0.4 μ m.
Composition and the heat resisting temperature (T10 value) of non-conductive particle, average circularity and the particle diameter distribution of the monomer that obtains using till the non-conductive particle from being formed up to of seeding polymerization composition granule (styrene, methacrylic acid, divinylbenzene, and vinyl xylene, ethyl vinyl benzene) are as shown in table 1.
The making of＜(4) acrylic polymer particle A 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 81.1 parts of n-butyl acrylates, 14.9 parts of acrylonitrile, 2-acrylamide-4.0 parts of 2-methyl propane sulfonic acids and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle A of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.Among the acrylic polymer particle A have sulfonic monomeric unit contain that ratio is 4.0%, sulfonicly contains that ratio is 1.56%, the acrylonitrile monemer unit contain that ratio is 14.9%, the ratio that contains of (methyl) acrylate monomeric units is 81.1%.
The making of＜(5) acrylic polymer particle B 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 81.9 parts of n-butyl acrylates, 15.1 parts of acrylonitrile, 3.0 parts of glycidyl methacrylate, and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain containing the aqueous dispersions of the acrylic polymer particle B of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.The monomeric unit with epoxy radicals among the acrylic polymer particle B contain that ratio is 3.0%, epoxy radicals contain that ratio is 0.91%, the acrylonitrile monemer unit contain that ratio is 15.1%, the ratio that contains of (methyl) acrylate monomeric units is 81.9%.
The manufacturing of＜(6) perforated membrane slurry 〉
As tackifier, using degree of etherification falling is that 0.8～1.0,1% solution viscosity is the carboxymethyl cellulose (Daicel1220 processed of Daicel chemical industry Co., Ltd.) of 10～20mPas, has prepared 1% aqueous solution.
Be that the mode of 83.1:6.15:6.15:4.6 is mixed in water with 1% aqueous solution of the aqueous dispersions of the acrylic polymer particle B that obtains in the aqueous dispersions of the acrylic polymer particle A that obtains in the aqueous dispersion of the non-conductive particle that obtains in the operation (3), the operation (4), the operation (5) and carboxy methyl cellulose with the solid constituent weight ratio, further add water as solvent, use ball mill to make its dispersion obtain the perforated membrane slurry.In addition, the content of the raw material (total amount of solid constituent) beyond the water in the perforated membrane slurry is 50 quality %.
In addition, the acrylic polymer particle A in the perforated membrane slurry with respect to the weight ratio (acrylic polymer particle A/ acrylic polymer particle B) of acrylic polymer particle B be 1, sulfonic group in the adhesive is 1.7 with respect to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The manufacturing that＜(7) are anodal 〉
Adding PVDF (Kynoar, Wu Yu chemistry corporate system, trade name: KF-1100) as binding agent for electrode as counting 3 parts mode with solid constituent conversion amount in 95 parts of the LiMn2O4s with spinel structure of positive active material, and then, add 2 parts of acetylene blacks, reach 20 parts of N-methyl pyrrolidones, they are mixed with planetary stirring machine, obtain the positive pole electrod composition (the anodal slurry of using) of pulp-like.This positive pole is coated with slurry on the one side of aluminium foil of thickness 18 μ m, at 120 ℃ down after dry 3 hours, carried out roll-in and make the positive pole with positive electrode active material layer that gross thickness is 100 μ m.
The manufacturing of＜(8) negative pole 〉
Will be as particle diameter 20 μ m, the specific area 4.2m of negative electrode active material 298 parts in the graphite of/g and solid constituent conversion amount are that 1 part the SBR as binding agent for electrode (styrene butadiene rubbers, glass transition temperature :-10 ℃) mixes, in this mixture, further mix 1.0 parts of carboxy methyl celluloses, further add water as solvent, they are mixed with planetary stirring machine, prepared the negative pole electrod composition (negative pole slurry) of pulp-like.This negative pole is coated with slurry on the one side of Copper Foil of thickness 18 μ m, at 120 ℃ down after dry 3 hours, carry out roll-in system, obtaining gross thickness is the negative pole with negative electrode active material layer of 60 μ m.
The manufacturing of＜(9) secondary battery separator (organic dividing plate of band perforated membrane) 〉
The polypropylene dividing plate processed (porosity 55%, thickness 25 μ m) of the individual layer that preparation is made by dry process is as organic dividing plate.The mode that with dried thickness is 5 μ m on the face of a side of this organic dividing plate uses the perforated membrane slurry that obtains in bar (wire bar) painting process (6) to obtain pulp layer, with pulp layer 50 ℃ dry 10 minutes down, form perforated membrane.Next, on the face of the opposite side of organic dividing plate, form perforated membrane similarly, obtain having on the two sides organic dividing plate of the band perforated membrane of perforated membrane.
＜(10) have the manufacturing of the secondary cell of secondary battery separator (organic dividing plate of band perforated membrane) 〉
The positive pole that obtains in the operation (7) is cut into the circle of diameter 13mm, obtains circular positive pole.The negative pole that obtains in the operation (8) is cut into the circle of diameter 14mm, has obtained circular negative pole.In addition, organic dividing plate of the band perforated membrane that obtains in the operation (9) is cut into the circle of diameter 18mm, has obtained organic dividing plate of circular band perforated membrane.
The positive pole of mounting circle on the inner bottom surface of packaging container outside the Coin shape of the stainless steel that is provided with polypropylene liner processed, organic dividing plate of the band perforated membrane of mounting circle thereon, further the negative pole of mounting circle thereon is accommodated in them in the container.The positive pole of mounting circle make the face of its aluminium foil one side towards the face of the bottom surface side of outer packaging container, positive electrode active material layer one side towards upside.The negative pole of mounting circle make the face of its negative electrode active material layer one side towards the face of organic bulkhead sides of the band perforated membrane of this circle, Copper Foil one side towards upside.With container 105 ℃ of following vacuumizes 24 hours.
Thereby in container, inject not residual air of electrolyte, cover the stainless lid of thickness 0.2mm and fixing outside on the packaging container via polypropylene liner processed, with the battery can sealing, made the lithium rechargeable battery (coin battery CR2032) of diameter 20mm, the about 3.2mm of thickness.As electrolyte, use in the mixed solvent that ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed with EC:DEC=1:2 (volumetric ratios under 20 ℃) and dissolve LiPF with the concentration of 1 mol 6The solution that forms.
＜(11) are estimated 〉
Cycle characteristics to uniformity and reliability, the mealiness that falls of the perforated membrane of organic dividing plate of the band perforated membrane that obtains and the secondary cell that obtains is estimated.Show the result in table 1.
(embodiment 2)
The perforated membrane slurry that obtains in the operation (6) of the one side of the negative electrode active material layer side of the negative pole that obtains in the operation (8) of embodiment 1 coating embodiment 1 also obtains pulp layer and makes it cover negative electrode active material layer fully and dried perforated membrane thickness is 5 μ m.Pulp layer was descended dry 10 minutes at 50 ℃, form perforated membrane, obtained the negative pole of band perforated membrane.The negative pole of the band perforated membrane that obtains has the such layer structure of (perforated membrane)/(negative electrode active material layer)/(Copper Foil).Uniformity and reliability, the mealiness that falls to the perforated membrane of the negative pole of the band perforated membrane that obtains are estimated.Show the result in table 1.
The organic dividing plate that replaces the band perforated membrane that obtains in the operation (9) of embodiment 1, used organic dividing plate (polypropylene of individual layer dividing plate processed, the porosity 55%, thickness 25 μ m, with the operation (9) of embodiment 1 in to be used as the dividing plate of organic dividing plate identical).
In addition, replace the negative pole that obtains 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 estimate.Show the result in table 1.In addition, when being positioned in the negative pole of the band perforated membrane of circle in the outer packaging container, with the one side of its perforated membrane side mode mounting towards the face of organic dividing plate one side of circle, Copper Foil one side towards upside.
(embodiment 3)
The acrylic polymer particle A that obtains in the operation (4) of replacement embodiment 1 uses following acrylic polymer particle A.In addition, the acrylic polymer particle B that obtains in the operation (5) of replacement embodiment 1 uses following acrylic polymer particle B.Use this acrylic polymer particle A and this acrylic polymer particle B to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.In addition, the acrylic polymer particle A in the perforated membrane slurry with respect to the weight ratio (acrylic polymer particle A/ acrylic polymer particle B) of acrylic polymer particle B be 1, sulfonic group in the adhesive is 1.7 with respect to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making of＜acrylic polymer particle A 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 89.0 parts of n-butyl acrylates, 7.0 parts of acrylonitrile, 2-acrylamide-4.0 parts of 2-methyl propane sulfonic acids and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle A1 of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.Among the acrylic polymer particle A have sulfonic monomeric unit contain that ratio is 4.0%, sulfonicly contains that ratio is 1.56%, the acrylonitrile monemer unit contain that ratio is 7%, the ratio that contains of (methyl) acrylate monomeric units is 89%.
The making of＜acrylic polymer particle B 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 90.0 parts of n-butyl acrylates, 7.0 parts of acrylonitrile, 3.0 parts of glycidyl methacrylate and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle B of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.The monomeric unit with epoxy radicals among the acrylic polymer particle B contain that ratio is 3.0%, epoxy radicals contain that ratio is 0.91%, the acrylonitrile monemer unit contain that ratio is 7%, the ratio that contains of (methyl) acrylate monomeric units is 90.0%.
(embodiment 4)
The acrylic polymer particle A that obtains in the operation (4) of replacement embodiment 1 uses following acrylic polymer particle A.In addition, the acrylic polymer particle B that obtains in the operation (5) of replacement embodiment 1 uses following acrylic polymer particle B.Use this acrylic polymer particle A and this acrylic polymer particle B to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
In addition, the acrylic polymer particle A in the perforated membrane slurry with respect to the weight ratio (acrylic polymer particle A/ acrylic polymer particle B) of acrylic polymer particle B be 1, sulfonic group in the adhesive is 1.7 with respect to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making of＜acrylic polymer particle A 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 66.1 parts of n-butyl acrylates, 29.9 parts of acrylonitrile, 2-acrylamide-4.0 parts of 2-methyl propane sulfonic acids and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle A of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.Among the acrylic polymer particle A have sulfonic monomeric unit contain that ratio is 4.0%, sulfonicly contains that ratio is 1.56%, the acrylonitrile monemer unit contain that ratio is 29.9%, the ratio that contains of (methyl) acrylate monomeric units is 66.1%.
The making of＜acrylic polymer particle B 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 66.8 parts of n-butyl acrylates, 30.2 parts of acrylonitrile, 3.0 parts of glycidyl methacrylate and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle B of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.The monomeric unit with epoxy radicals among the acrylic polymer particle B contain that ratio is 3.0%, epoxy radicals contain that ratio is 0.91%, the acrylonitrile monemer unit contain that ratio is 30.2%, the ratio that contains of (methyl) acrylate monomeric units is 66.8%.
(embodiment 5)
The non-conductive particle that obtains in operation (1)～(3) of replacement embodiment 1, use following non-conductive particle to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
The manufacturing of＜non-conductive particle 〉
In having the reactor of mixer, put into the operation (1) of embodiment 1, (2) aqueous dispersion of the seeding polymerization composition granule B that obtains in is counted 10 parts with solid constituent benchmark (being seeding polymerization composition granule B weight basis), 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) 33 parts, 57 parts of vinyl xylene, ethyl vinyl benzene, 1 part of neopelex, peroxidating (2 ethyl hexanoic acid) tert-butyl ester (day oily society system as polymerization initiator, trade name: Perbutyl O) 5 parts and ion exchange water are 200 parts, stirred 12 hours down at 35 ℃, make seeding polymerization composition granule B absorb monomer mixture and polymerization initiator fully thus.Then, with it 90 ℃ of following polymerizations 4 hours.Then, import steam and remove unreacted monomer.
Thus, obtain the aqueous dispersion of the non-conductive particle of average grain diameter 0.4 μ m.
Composition and the heat resisting temperature (T10 value) of non-conductive particle, average circularity and the particle diameter distribution of the monomer that obtains using till the non-conductive particle from being formed up to of seeding polymerization composition granule (styrene, methacrylic acid, divinylbenzene, and vinyl xylene, ethyl vinyl benzene) are as shown in table 1.
(embodiment 6)
The non-conductive particle that obtains in operation (1)～(3) of replacement embodiment 1, use following non-conductive particle to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
The manufacturing of＜seeding polymerization composition granule A 〉
In having the reactor of mixer, put into 95 parts of styrene, 5 parts of divinylbenzenes, 1.0 parts of neopelexes, 100 parts of ion exchange waters, reach 0.5 part of potassium peroxydisulfate, 80 ℃ of following polymerizations 8 hours.Thus, obtain the aqueous dispersion of the seeding polymerization composition granule A of average grain diameter 60nm.
The manufacturing of＜non-conductive particle 〉
In having the reactor of mixer, use the aqueous dispersion of above-mentioned seeding polymerization composition granule A, in addition, similarly operate with operation (2), (3) of embodiment 1, obtain average circularity and be the aqueous dispersion of 0.91 non-conductive particle.The composition of the monomer that obtains using till the non-conductive particle from being formed up to of seeding polymerization composition granule (styrene, methacrylic acid, divinylbenzene, and vinyl xylene, ethyl vinyl benzene) and heat resisting temperature (T10 value), average grain diameter and the particle diameter distribution of non-conductive particle are as shown in table 1.
(embodiment 7)
The acrylic polymer particle A that obtains in the operation (4) of replacement embodiment 1 uses following acrylic polymer particle A.In addition, the acrylic polymer particle B that obtains in the operation (5) of replacement embodiment 1 uses following acrylic polymer particle B.Use this acrylic polymer particle A and this acrylic polymer particle B to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
In addition, the acrylic polymer particle A in the perforated membrane slurry with respect to the weight ratio (acrylic polymer particle A/ acrylic polymer particle B) of acrylic polymer particle B be 1, sulfonic group in the adhesive is 3.4 with respect to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making of＜acrylic polymer particle A 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 80.2 parts of n-butyl acrylates, 14.8 parts of acrylonitrile, 2-acrylamide-5.0 parts of 2-methyl propane sulfonic acids and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle A of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.Among the acrylic polymer particle A have sulfonic monomeric unit contain that ratio is 5.0%, sulfonicly contains that ratio is 1.95%, the acrylonitrile monemer unit contain that ratio is 14.8%, the ratio that contains of (methyl) acrylate monomeric units is 80.2%.
The making of＜acrylic polymer particle B 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 82.9 parts of n-butyl acrylates, 15.2 parts of acrylonitrile, 1.9 parts of glycidyl methacrylate, and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle B of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.The monomeric unit with epoxy radicals among the acrylic polymer particle B contain that ratio is 1.9%, epoxy radicals contain that ratio is 0.58%, the acrylonitrile monemer unit contain that ratio is 15.2%, the ratio that contains of (methyl) acrylate monomeric units is 82.9%.
(embodiment 8)
The acrylic polymer particle A that obtains in the operation (4) of replacement embodiment 1 uses following acrylic polymer particle A.In addition, the acrylic polymer particle B that obtains in the operation (5) of replacement embodiment 1 uses following acrylic polymer particle B.Use this acrylic polymer particle A and this acrylic polymer particle B to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
In addition, the acrylic polymer particle A in the perforated membrane slurry with respect to the weight ratio (acrylic polymer particle A/ acrylic polymer particle B) of acrylic polymer particle B be 1, sulfonic group in the adhesive is 0.6 with respect to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making of＜acrylic polymer particle A 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 82.6 parts of n-butyl acrylates, 15.2 parts of acrylonitrile, 2-acrylamide-2.2 parts of 2-methyl propane sulfonic acids and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle A of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.Among the acrylic polymer particle A have sulfonic monomeric unit contain that ratio is 2.2%, sulfonicly contains that ratio is 0.86%, the acrylonitrile monemer unit contain that ratio is 15.2%, the ratio that contains of (methyl) acrylate monomeric units is 82.6%.
The making of＜acrylic polymer particle B 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 80.5 parts of n-butyl acrylates, 14.8 parts of acrylonitrile, 4.7 parts of glycidyl methacrylate, and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle B of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.The monomeric unit with epoxy radicals among the acrylic polymer particle B contain that ratio is 4.7%, epoxy radicals contain that ratio is 1.42%, the acrylonitrile monemer unit contain that ratio is 14.8%, the ratio that contains of (methyl) acrylate monomeric units is 80.5%.
(embodiment 9)
The acrylic polymer particle A that obtains in the operation (4) of replacement embodiment 1 uses following acrylic polymer particle A.In addition, the acrylic polymer particle B that obtains in the operation (5) of replacement embodiment 1 uses following acrylic polymer particle B.Use this acrylic polymer particle A and this acrylic polymer particle B to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
In addition, the acrylic polymer particle A in the perforated membrane slurry with respect to the weight ratio (acrylic polymer particle A/ acrylic polymer particle B) of acrylic polymer particle B be 1, sulfonic group in the adhesive is 2.8 with respect to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making of＜acrylic polymer particle A 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 76.2 parts of n-butyl acrylates, 14.0 parts of acrylonitrile, 2-acrylamide-9.8 parts of 2-methyl propane sulfonic acids and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle A of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.Among the acrylic polymer particle A have sulfonic monomeric unit contain that ratio is 9.8%, sulfonicly contains that ratio is 3.82%, the acrylonitrile monemer unit contain that ratio is 14.0%, the ratio that contains of (methyl) acrylate monomeric units is 76.2%.
The making of＜acrylic polymer particle B 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 80.6 parts of n-butyl acrylates, 14.9 parts of acrylonitrile, 4.5 parts of glycidyl methacrylate, and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle B of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.The monomeric unit with epoxy radicals among the acrylic polymer particle B contain that ratio is 4.5%, epoxy radicals contain that ratio is 1.36%, the acrylonitrile monemer unit contain that ratio is 14.9%, the ratio that contains of (methyl) acrylate monomeric units is 80.6%.
(embodiment 10)
The acrylic polymer particle A that obtains in the operation (4) of replacement embodiment 1 uses following acrylic polymer particle A.In addition, the acrylic polymer particle B that obtains in the operation (5) of replacement embodiment 1 uses following acrylic polymer particle B.Use this acrylic polymer particle A and this acrylic polymer particle B to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
In addition, the acrylic polymer particle A in the perforated membrane slurry with respect to the weight ratio (acrylic polymer particle A/ acrylic polymer particle B) of acrylic polymer particle B be 1, sulfonic group in the adhesive is 1.8 with respect to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making of＜acrylic polymer particle A 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 83.6 parts of n-butyl acrylates, 15.4 parts of acrylonitrile, 2-acrylamide-1.0 parts of 2-methyl propane sulfonic acids and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle A of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.Among the acrylic polymer particle A have sulfonic monomeric unit contain that ratio is 1.0%, sulfonicly contains that ratio is 0.39%, the acrylonitrile monemer unit contain that ratio is 15.4%, the ratio that contains of (methyl) acrylate monomeric units is 83.6%.
The making of＜acrylic polymer particle B 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 83.9 parts of n-butyl acrylates, 15.4 parts of acrylonitrile, 0.7 part of glycidyl methacrylate, and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle B of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.The monomeric unit with epoxy radicals among the acrylic polymer particle B contain that ratio is 0.7%, epoxy radicals contain that ratio is 0.21%, the acrylonitrile monemer unit contain that ratio is 15.4%, the ratio that contains of (methyl) acrylate monomeric units is 83.9%.
(embodiment 11)
The acrylic polymer particle A that obtains in the operation (4) of replacement embodiment 1 uses following acrylic polymer particle A.In addition, the acrylic polymer particle B that obtains in the operation (5) of replacement embodiment 1 uses following acrylic polymer particle B.Use this acrylic polymer particle A and this acrylic polymer particle B to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
In addition, the acrylic polymer particle A in the perforated membrane slurry with respect to the weight ratio (acrylic polymer particle A/ acrylic polymer particle B) of acrylic polymer particle B be 1, sulfonic group in the adhesive is 1.5 with respect to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The making of＜acrylic polymer particle A 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 77.9 parts of n-butyl acrylates, 14.4 parts of acrylonitrile, 2-acrylamide-7.7 parts of 2-methyl propane sulfonic acids and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle A of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.Among the acrylic polymer particle A have sulfonic monomeric unit contain that ratio is 7.7%, sulfonicly contains that ratio is 3.00%, the acrylonitrile monemer unit contain that ratio is 14.4%, the ratio that contains of (methyl) acrylate monomeric units is 77.9%.
The making of＜acrylic polymer particle B 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 78.7 parts of n-butyl acrylates, 14.5 parts of acrylonitrile, 6.8 parts of glycidyl methacrylate and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle B of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.The monomeric unit with epoxy radicals among the acrylic polymer particle B contain that ratio is 6.8%, epoxy radicals contain that ratio is 2.06%, the acrylonitrile monemer unit contain that ratio is 14.5%, the ratio that contains of (methyl) acrylate monomeric units is 78.7%.
(embodiment 12)
The non-conductive particle that obtains in operation (1)～(3) of replacement embodiment 1, use following non-conductive particle to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
The manufacturing of＜seeding polymerization composition granule C 〉
The aqueous dispersion of putting into the seeding polymerization composition granule B that the operation (2) of embodiment 1 obtains in having the reactor of mixer is counted 2 parts, 0.2 part of neopelex, 0.5 part of potassium peroxydisulfate, and 100 parts of ion exchange waters with solid constituent benchmark (being seeding polymerization composition granule B weight basis), mix, obtain mixture, be warming up to 80 ℃.On the other hand, 97 parts of benzene mixed ethene, 3 parts of methacrylic acids, 4 parts of uncle's lauryl mercaptans, 0.5 part of neopelex, and 100 parts of ion exchange waters in another container, the dispersion of preparation monomer mixture.Be added in the said mixture continuously and carry out polymerization through 4 hours dispersions with this monomer mixture.The temperature of the reaction system in the continuous interpolation process of the dispersion of monomer mixture remains 80 ℃, reacts.After adding end continuously, further continue reaction 3 hours down at 90 ℃.
Thus, obtain the aqueous dispersion of the seeding polymerization composition granule C of average grain diameter 400nm.
The manufacturing of＜non-conductive particle 〉
The seeding polymerization composition granule B that obtains in the operation (2) of replacement embodiment 1 uses above-mentioned seeding polymerization composition granule C to carry out the operation same with the operation (3) of embodiment 1, obtains the aqueous dispersion of the non-conductive particle of average grain diameter 700nm.Use composition and the heat resisting temperature (T10 value) of non-conductive particle, average circularity and the particle diameter distribution of the monomer that uses till the non-conductive particle (styrene, methacrylic acid, divinylbenzene, and vinyl xylene, ethyl vinyl benzene) as shown in table 1 from being formed up to of seed polymer.
(embodiment 13)
The non-conductive particle that obtains in operation (1)～(3) of replacement embodiment 1, use following non-conductive particle to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
The manufacturing of＜non-conductive particle 〉
The middle monomer mixture that uses of operation (3) that replaces embodiment 1, use mixture (the monomer mixing ratio: divinylbenzene/vinyl xylene, ethyl vinyl benzene=82/18, chemical company of Nippon Steel system, goods name: DVB-810) 72 parts, and 18 parts of methyl methacrylates of divinylbenzene and vinyl xylene, ethyl vinyl benzene, in addition, carry out the operation same with the operation (3) of embodiment 1, obtain the aqueous dispersion of the non-conductive particle of average grain diameter 400nm.Composition and the heat resisting temperature (T10 value) of non-conductive particle, average circularity and the particle diameter distribution of the monomer that obtains using till the non-conductive particle from being formed up to of seeding polymerization composition granule (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene, and methyl methacrylate) are as shown in table 1.
(embodiment 14)
The making of the NMP dispersion of＜non-conductive particle 〉
After 200 parts of 100 parts of (solid component concentration is 20%) middle interpolation N-N-methyl-2-2-pyrrolidone N-s of the aqueous dispersion of the non-conductive particle that in the operation (3) of embodiment 1, obtains (NMP) and the abundant mixing, water and the NMP in the system removed in distillation under 90 ℃ of reduced pressure atmosphere, obtains the NMP dispersion (solid component concentration is 20%) of non-conductive particle.
The making of the NMP dispersion of＜acrylic polymer particle A 〉
After 100 parts of (solid constituent is 40%) middle NMP that add 760 parts of the aqueous dispersion of the acrylic polymer particle A that obtains in the operation (4) of embodiment 1 also fully mix, water and the NMP in the system removed in distillation under 90 ℃ of reduced pressure atmosphere, obtains the NMP dispersion (solid constituent is 10%) of acrylic polymer particle A.
The making of the NMP dispersion of＜acrylic polymer particle B 〉
After 100 parts of (solid constituent is 40%) middle NMP that add 760 parts of the aqueous dispersion of the acrylic polymer particle B that obtains in the operation (5) of embodiment 1 also fully mix, water and the NMP in the system removed in distillation under 90 ℃ of reduced pressure atmosphere, obtains the NMP dispersion (solid constituent is 10%) of acrylic polymer particle B.
The manufacturing of＜perforated membrane slurry 〉
With the NMP dispersion of the NMP dispersion of the non-conductive particle that obtains in the above-mentioned operation, acrylic polymer particle A and, the NMP dispersion of acrylic polymer particle B mixes than the mode that is 87.0:6.5:6.5 with solid constituent, obtains the perforated membrane slurry of solid component concentration 18%.
In addition, the acrylic polymer particle A in the perforated membrane slurry with respect to the weight ratio (acrylic polymer particle A/ acrylic polymer particle B) of acrylic polymer particle B be 1, sulfonic group in the adhesive is 1.7 with respect to the weight ratio (sulfonic group/epoxy radicals) of epoxy radicals.
The manufacturing of the negative pole of＜band perforated membrane 〉
In the operation (8) of embodiment 1 thus in the perforated membrane slurry that obtains in the above-mentioned operation of the one side coating of negative electrode active material layer side of the negative pole that obtains and obtain that pulp layer makes it cover negative electrode active material layer fully, dried perforated membrane thickness is 5 μ m.Pulp layer was descended dry 10 minutes at 100 ℃, form perforated membrane, obtain the negative pole with perforated membrane.The negative pole of the band perforated membrane that obtains has the such layer structure of (perforated membrane)/(negative electrode active material layer)/(Copper Foil).Uniformity and reliability, the mealiness that falls to the perforated membrane of the negative pole of the band perforated membrane that obtains are estimated.Show the result in table 1.
＜have a manufacturing of secondary cell of the negative pole of band perforated membrane 〉
The organic dividing plate that replaces the band perforated membrane that obtains in the operation (9) of embodiment 1, use organic dividing plate (polypropylene of individual layer dividing plate processed, the porosity 55%, thickness 25 μ m, with the operation (9) of embodiment 1 in to be used as the dividing plate of organic dividing plate identical).
In addition, replace the negative pole that obtains 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 estimate.Show the result in table 1.In addition, outside the negative pole with the band perforated membrane of circle is positioned in the packaging container time, it is with the one side of the perforated membrane side mode mounting towards the one side of organic bulkhead sides of circle, Copper Foil side towards upside.
(comparative example 1)
The acrylic polymer particle A, the B that obtain in the operation (4) of replacement embodiment 1, (5), use following acrylic polymer particle C to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
The making of＜acrylic polymer particle C 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 81.5 parts of n-butyl acrylates, 15.0 parts of acrylonitrile, 2-acrylamide-2.0 parts of 2-methyl propane sulfonic acids, 1.5 parts of glycidyl methacrylate and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle C of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.In addition, acrylic polymer particle C has sulfonic group and epoxy radicals, and sulfonic among the acrylic polymer particle C contains that ratio is 0.78%, the ratio that contains of epoxy radicals is 0.45%.
(comparative example 2)
Do not use the acrylic polymer particle A that obtains in the operation (4) of embodiment 1, the acrylic polymer particle B that obtains in the operation (5) of replacement embodiment 1, use following acrylic polymer particle B to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
The making of＜acrylic polymer particle B 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 78.7 parts of n-butyl acrylates, 14.5 parts of acrylonitrile, 6.8 parts of glycidyl methacrylate, and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle B of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.The monomeric unit with epoxy radicals among the acrylic polymer particle B contain that ratio is 6.8%, epoxy radicals contain that ratio is 2.06%, the acrylonitrile monemer unit contain that ratio is 14.5%, the ratio that contains of (methyl) acrylate monomeric units is 78.7%.
(comparative example 3)
Do not use the acrylic polymer particle B that obtains in the operation (5) of embodiment 1, the acrylic polymer particle A that obtains in the operation (4) of replacement embodiment 1, use following acrylic polymer particle A to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.
The making of＜acrylic polymer particle A 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 78.7 parts of n-butyl acrylates, 14.5 parts of acrylonitrile, 2-acrylamide-6.8 parts of 2-methyl propane sulfonic acids and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle A of average grain diameter 0.18 μ m.In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.Among the acrylic polymer particle A have sulfonic monomeric unit contain that ratio is 6.8%, sulfonicly contains that ratio is 2.65%, the acrylonitrile monemer unit contain that ratio is 14.5%, the ratio that contains of (methyl) acrylate monomeric units is 78.7%.
(comparative example 4)
The acrylic polymer particle A that obtains in the operation (4) of replacement embodiment 1, use following acrylic polymer particle A to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.In addition, the same particle of acrylic polymer particle B that obtains in the operation (5) of acrylic polymer particle B use and embodiment 1.
The making of＜acrylic polymer particle A 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 84.5 parts of n-butyl acrylates, 15.5 parts of acrylonitrile and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle A of average grain diameter 0.18 μ m.
In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.Among the acrylic polymer particle A have sulfonic monomeric unit contain that ratio is 0%, sulfonicly contains that ratio is 0%, the acrylonitrile monemer unit contain that ratio is 15.5%, the ratio that contains of (methyl) acrylate monomeric units is 84.5%.
(comparative example 5)
The acrylic polymer particle B that obtains in the operation (5) of replacement embodiment 1, use following acrylic polymer particle B to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtain with organic dividing plate and the secondary cell of perforated membrane and estimate.Show the result in table 1.In addition, the same particle of acrylic polymer particle A that obtains in the operation (4) of acrylic polymer particle A use and embodiment 1.
The making of＜acrylic polymer particle B 〉
In the autoclave of band mixer, put into 300 parts of ion exchange waters, 84.5 parts of n-butyl acrylates, 15.5 parts of acrylonitrile and as 0.05 part of uncle's lauryl mercaptan of molecular weight regulator, as 0.3 part of the potassium peroxydisulfate of polymerization initiator, as 1.0 parts of the neopelexes of emulsifying agent, after fully stirring, be heated to 70 ℃ and carry out polymerization, obtain containing the aqueous polymer dispersion of unreacted monomer.Then, this aqueous polymer dispersion is cooled to 25 ℃, after adding ammoniacal liquor therein pH being adjusted to 7, imports steam and remove unreacted monomer, obtain the aqueous dispersions of the acrylic polymer particle B of average grain diameter 0.18 μ m.
In addition, the polymerisation conversion of being obtained by solid component concentration is approximately 99%.
The monomeric unit with epoxy radicals among the acrylic polymer particle B contain that ratio is 0%, epoxy radicals contain that ratio is 0%, the acrylonitrile monemer unit contain that ratio is 15.5%, the ratio that contains of (methyl) acrylate monomeric units is 84.5%.
(comparative example 6)
Except the acrylic polymer particle A, the B that obtain in the operation (4) that replaces embodiment 2, (5), use the acrylate copolymer C that obtains in the comparative example 1 to make beyond the perforated membrane slurry, carry out operation similarly to Example 2, obtain with negative pole and the secondary cell of perforated membrane and estimate.Show the result in table 1.
According to the result of table 1, can followingly describe.
Use comprises and contains the non-conductive particle of organic macromolecule and adhesive forms uniformity, the reliability of the perforated membrane of the secondary battery separator with secondary cell perforated membrane, electrode for secondary battery and secondary cell that the secondary cell perforated membrane slurry (embodiment 1～14) of (this adhesive comprises the acrylic polymer particle B that has sulfonic acrylic polymer particle A and have epoxy radicals) forms, the balance excellence of cycle characteristics.
On the other hand, use the adhesive case (comparative example 1,6) in a polymer beads, have sulfonic group and epoxy radicals, using under the situation (comparative example 2,4) that does not have sulfonic adhesive and the situation (comparative example 3,5) of the using the adhesive that does not have epoxy radicals the balanced differences of the uniformity of perforated membrane, reliability, cycle characteristics.

Claims (13)

1. secondary cell perforated membrane slurry, it comprises and contains the non-conductive particle of organic macromolecule, adhesive and solvent and form,
This adhesive contains:
Have sulfonic acrylic polymer particle A, and
Acrylic polymer particle B with epoxy radicals.
2. secondary cell perforated membrane slurry according to claim 1, wherein,
With respect to all solids composition 100 quality %, the ratio that contains of described non-conductive particle is 70～97 quality %, and the ratio that contains of described adhesive is 0.5～20 quality %.
3. secondary cell perforated membrane slurry according to claim 1 and 2, wherein,
Described acrylic polymer particle A and described acrylic polymer particle B contains (methyl) acrylonitrile monemer unit and (methyl) acrylate monomeric units forms.
4. secondary cell perforated membrane slurry according to claim 3, wherein,
In described acrylic polymer particle A and described acrylic polymer particle B, the ratio that contains of (methyl) acrylonitrile monemer unit in the polymer beads is 2.5～40 quality %, and the ratio that contains of (methyl) acrylate monomeric units in the polymer beads is 60～97.5 quality %.
5. according to each described secondary cell perforated membrane slurry in the claim 1～4, wherein,
Described acrylic polymer particle A is that acrylic polymer particle A/ acrylic polymer particle B is 0.3～3 with respect to the weight ratio of described acrylic polymer particle B.
6. according to each described secondary cell perforated membrane slurry in the claim 1～5, wherein,
The sulfonic ratio that contains among the described acrylic polymer particle A is 0.04～5.8 quality %, and the ratio that contains of the epoxy radicals among the described acrylic polymer particle B is 0.03～3.0 quality %.
7. according to each described secondary cell perforated membrane slurry in the claim 1～6, wherein,
In described adhesive, the sulfonic group among the described acrylic polymer particle A is that sulfonic group/epoxy radicals is 0.2～3 with respect to the weight ratio of the epoxy radicals among the described acrylic polymer particle B.
8. according to each described secondary cell perforated membrane slurry in the claim 1～7, wherein,
Under blanket of nitrogen during with the heating of 10 ℃/minute of programming rates, the temperature that the loss of weight ratio of described non-conductive particle reaches 10 quality % is more than 250 ℃ with thermobalance,
The average grain diameter of this non-conductive particle is 0.1～2.0 μ m,
The average circularity of this non-conductive particle is 0.900～0.995.
9. secondary cell perforated membrane, it is by forming membranaceous and dry obtaining with each described secondary cell perforated membrane slurry in the claim 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 described secondary cell perforated membrane of the lip-deep claim 9 of this electrode active material layer.
11. a secondary battery separator, it comprises:
Organic dividing plate,
Be stacked in the described secondary cell perforated membrane of claim 9 on this organic dividing plate.
12. a 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 requirement 9 described secondary cell perforated membranes of having the right.
13. the manufacture method of a secondary cell perforated membrane, it comprises:
Each described secondary cell perforated membrane slurry in basis material coating claim 1～8 carries out dry operation then.
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