CN103238234A - Secondary-battery porous-embrane slurry, secondary-battery porous membrane, secondary-battery electrode, secondary-battery separator, and secondary battery - Google Patents

Secondary-battery porous-embrane slurry, secondary-battery porous membrane, secondary-battery electrode, secondary-battery separator, and secondary battery Download PDF

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CN103238234A
CN103238234A CN2011800577884A CN201180057788A CN103238234A CN 103238234 A CN103238234 A CN 103238234A CN 2011800577884 A CN2011800577884 A CN 2011800577884A CN 201180057788 A CN201180057788 A CN 201180057788A CN 103238234 A CN103238234 A CN 103238234A
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perforated membrane
adhesive
secondary cell
monomer
conductive organic
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CN103238234B (en
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金田拓也
松村卓
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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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M50/443—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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)

Abstract

[Problem] To provide a highly flexible secondary-battery porous membrane that can prevent powder loss, has a low moisture content, 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 organic particles. Also, to provide nonconductive organic particles that contain little metallic foreign material and are suitable for use in a secondary-battery porous membrane. Therefore, the secondary-battery porous-membrane slurry in the present invention is characterized by containing: a binder comprising a vinyl-monomer polymerization unit that has a thermally crosslinkable group; nonconductive organic particles that have functional groups that can be crosslinked with said thermally crosslinkable group; and a solvent.

Description

Secondary cell perforated membrane slurry, secondary cell perforated membrane, electrode for secondary battery, secondary battery separator and secondary cell
Technical field
The present invention relates to a kind of secondary cell perforated membrane slurry, more specifically, relate to a kind of for the manufacture of the electrode that is formed at lithium rechargeable battery or baffle surface, flexibility is high and can help the secondary cell perforated membrane slurry of secondary cell perforated membrane of improvement of the cycle characteristics of battery.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 demonstrates the highest energy density, particularly the miniaturized electronics purposes that are used for more.In addition, except small-sized purposes, also expect to launch to automotive field.Wherein, the long lifetime of expectation lithium rechargeable battery and the further raising of fail safe.
In order to prevent the short circuit between positive pole and the negative pole, use the organic dividing plates of TPO such as polyethylene, polypropylene in the lithium rechargeable battery usually.Because the organic dividing plate of TPO has rerum natura in fusion below 200 ℃, therefore, under the situation that battery reaches a high temperature because of inner and/or outside stimulation, the contraction, fusion of organic dividing plate etc. can take place, cause the volume of organic dividing plate to change.Its result might cause the short circuit of positive pole and negative pole, set off an explosion etc. because of release of electric energy etc.
In order to solve such problem of using the organic dividing plate of TPO that results from, following proposal has been proposed: on the organic dividing plate of TPO or electrode (anodal, negative pole) superimposed layer contain the layer (perforated membrane) of non-conductive particle such as inorganic particle.In addition, the thermal runaway for the abnormal response that prevents battery causes has proposed a kind of perforated membrane, and described perforated membrane contains the polymer beads that the polymer beads of fusion, the swellbility in electrolyte rise because being heated takes place because being heated.It is considered to have following function: in the temperature of secondary cell because under the situation of short circuit etc. and abnormal ascending, this polymer beads stops up fine hole in the perforated membrane because of fusion or swelling, stop interelectrode ion to pass through thus, therefore have the function (cut-out function) of the further rising of blocking-up electric current, inhibition temperature.
For example in patent documentation 1, put down in writing a kind of perforated membrane, in order to improve fail safe, the organic fine particles that makes this perforated membrane contain the heat-resistant resin particulate and have the cut-out function.In addition, wherein also put down in writing use ethane-acetic acid ethyenyl ester polymer as the perforated membrane adhesive.
Put down in writing in the patent documentation 2 by the water dispersible acroleic acid polymerization composition granule with possess hydrophilic property groups such as sulfonic acid and prevented that as adhesive non-conductive particle is from the method for the powder that falls of perforated membrane.In addition, also put down in writing following content: further have crosslinkable groups by making in the water dispersible acroleic acid polymerization composition granule, can have tough and tensile and soft perforated membrane.
Put down in writing in the patent documentation 3 a kind of use aluminium oxide, titanium oxide as inorganic filler, use polyvinyl alcohol, Styrene-Butadiene as the perforated membrane of adhesive.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-139978 communique
Patent documentation 2: open WO2009/123168 number of international monopoly
Patent documentation 3: TOHKEMY 2008-210794 communique
Summary of the invention
The problem that invention will solve
Yet, according to the inventor's research, therefore the perforated membrane of record in the patent documentation 1 is owing to use the ethane-acetic acid ethyenyl ester polymer as adhesive,, 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, the flexibility variation of perforated membrane sometimes.In addition, if use the ethane-acetic acid ethyenyl ester polymer as adhesive, then can't keep the caking property of heat-resistant resin particulate and organic fine particles sometimes fully, may cause this particulate to break away from (powder falls) from perforated membrane.
With regard to the perforated membrane of record in the patent documentation 2, though the excellent dispersion of known non-conductive particle in the perforated membrane slurry, but in the acroleic acid polymerization composition granule as adhesive, contain under the situation of hydrophilic radical and crosslinkable groups, have reactive functional group mutually owing to exist, thereby have the tendency that cross-linking reaction takes place in the slurry manufacturing process.Therefore, the screening characteristics of slurry in time process and become unstable, its result may cause the flexibility of perforated membrane to become insufficient.
With regard to the perforated membrane of record in the patent documentation 3, may cause cycle characteristics to reduce because side reaction takes place in battery moisture contained in the perforated membrane, in addition, may cause cycle characteristics to reduce because the ion stripping takes place in battery metal impurities contained in the inorganic filler.
Therefore, the secondary cell perforated membrane that the object of the present invention is to provide a kind of secondary cell perforated membrane slurry of the excellent dispersion of using screening characteristics and non-conductive organic granular to make, this secondary cell perforated membrane can make the cycle characteristics of gained secondary cell improve, its flexibility height, can prevent the falling stop powder, and the amount of moisture that contains is few.
For this reason, the inventor studies, and found that, by using specific adhesive and specific non-conductive organic granular, can obtain flexibility and the perforated membrane of the mealiness excellence that falls.That is to say, by using specific adhesive and specific non-conductive organic granular, can suppress the cross-linking reaction in the slurry manufacturing process, reduce the tackify of slurry etc.Therefore, the dispersiveness of non-conductive organic granular in the perforated membrane slurry and the screening characteristics of perforated membrane slurry can be improved, the high perforated membrane of flexibility can be obtained.In addition, owing to be used for forming cross-linked structure between adhesive of the present invention and the non-conductive organic granular, therefore, the caking property of adhesive and non-conductive organic granular becomes well, can prevent that non-conductive organic granular breaks away from (powder falls) from perforated membrane.In addition, because the non-conductive organic granular among the present invention does not have the ion stripping from inorganic filler, the water content of perforated membrane is few, therefore, also can not make the battery behavior variation.In addition, the inventor also finds, the dispersiveness by improving the non-conductive organic granular in the perforated membrane slurry and the screening characteristics of perforated membrane slurry not only can improve the productivity of perforated membrane, can also improve the cycle characteristics of the secondary cell that uses this perforated membrane.
The method of dealing with problems
In order to solve above-mentioned problem, purport of the present invention is as described below.
(1) a kind of secondary cell perforated membrane slurry, it contains: comprise the polymerized unit of the vinyl monomer with heat cross-linking group adhesive, have can with non-conductive organic granular and the solvent of the crosslinked functional group of this heat cross-linking group.
(2) according to (1) described secondary cell perforated membrane slurry, wherein, described adhesive also contains polymerized unit and the α of (methyl) acrylate monomer, the polymerized unit of alpha, beta-unsaturated nitriles monomer,
In whole polymerized units, the ratio that contains of the polymerized unit of described vinyl monomer with heat cross-linking group is 0.1～10 quality %, the ratio that contains of the polymerized unit of described (methyl) acrylate monomer is 50～98 quality %, described α, the polymerized unit of alpha, beta-unsaturated nitriles monomer are 1.0～50 quality %.
(3) according to (1) or (2) described secondary cell perforated membrane slurry, wherein, described heat cross-linking group is epoxy radicals or pi-allyl.
(4) according to each described secondary cell perforated membrane slurry in (1)～(3), wherein, the average grain diameter of described non-conductive organic granular is 0.1～2.0 μ m,
And 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 organic granular reaches 10 quality % is more than 250 ℃ with thermobalance.
(5) according to each described secondary cell perforated membrane slurry in (1)～(4), wherein, with respect to non-conductive organic granular, described can be 0.008～0.240mmol/g with the content of the crosslinked functional group of heat cross-linking group.
(6) according to each described secondary cell perforated membrane slurry in (1)～(5), wherein, described can be sulfonic group or phosphate with the crosslinked functional group of heat cross-linking group.
(7) 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)～(6).
(8) a kind of secondary cell perforated membrane, it comprises: comprise the vinyl monomer with heat cross-linking group polymerized unit adhesive and have can with the non-conductive organic granular of the crosslinked functional group of this heat cross-linking group,
Between described adhesive and described non-conductive organic granular, has cross-linked structure.
(9) a kind of electrode for secondary battery, it contains: collector body, be attached to this collector body and comprise electrode active material and the electrode active material layer of binding agent for electrode and be stacked in this electrode active material layer lip-deep (7) or (8) described secondary cell perforated membrane.
(10) a kind of secondary battery separator, it contains organic dividing plate, is stacked in (7) or (8) the described secondary cell perforated membrane on this organic dividing plate.
(11) 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 (7) or (8) described secondary cell perforated membrane.
The effect of invention
According to the present invention, a kind of secondary cell perforated membrane slurry can be provided, described secondary cell perforated membrane slurry is for the manufacture of the secondary cell perforated membrane, adhesive and the specific non-conductive organic granular of described secondary cell perforated membrane by containing specific composition, flexibility and the mealiness excellence that falls can help the raising of the cycle characteristics of secondary cell.In addition, the dispersiveness of this perforated membrane slurry and screening characteristics excellence.In addition, because the water content of the secondary cell perforated membrane that this perforated membrane slurry of use is made is few, therefore, the deterioration of battery behavior can not take place also.In addition, by this perforated membrane is stacked on electrode surface, can prevent the disengaging of electrode active material.In addition, can provide a kind of non-conductive organic granular that the metal ion stripping can not take place in secondary cell.
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 (following also note is made " perforated membrane slurry ") is for being used to form the slurry of secondary cell perforated membrane described later.The perforated membrane slurry contains adhesive and the specific non-conductive organic granular of specific composition, with as this adhesive of solid constituent, this non-conductive organic granular and arbitrarily composition be dispersed in the solvent and obtain.
(adhesive)
Be used for the polymerized unit that adhesive of the present invention comprises the vinyl monomer with heat cross-linking group.In the present invention, comprise the adhesive that the polymerized unit of the vinyl monomer with heat cross-linking group forms by use, can give good caking property to adhesive, can improve the reactivity with non-conductive organic granular described later simultaneously.Its result can obtain the high and few perforated membrane of the powder that falls of caking property, in addition, can use the cycle characteristics of the secondary cell of this perforated membrane to improve.
As being used for the heat cross-linking group with vinyl monomer of heat cross-linking group of the present invention, can enumerate epoxy radicals, N-methylol amide base, Azoles quinoline base, pi-allyl, NCO, oxa-cyclobutyl, alkoxysilane group etc.Wherein, because adjusting crosslinked and crosslink density is easy, therefore preferred epoxy radicals or pi-allyl, preferred especially epoxy radicals.Need to prove that the kind of bridging property functional group can be a kind, also can be for more than 2 kinds.
As the vinyl monomer with epoxy radicals, for example can enumerate the monomer that contains carbon-to-carbon double bond and epoxy radicals.
As the monomer that contains carbon-to-carbon double bond and epoxy radicals, for example can enumerate: unsaturated glycidol ethers such as vinyl glycidyl ether, allyl glycidyl ether, cyclobutenyl glycidol ether, o-allyl base glycidol 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 etc.
As the vinyl monomer with N-methylol amide base, for example can enumerate: N-methylol (methyl) acrylamide etc. has (methyl) acrylic amide of methylol etc.
As having
Figure BDA00003276409000051
The vinyl monomer of azoles quinoline base for example can be enumerated: 2-vinyl-2-
Figure BDA00003276409000052
Azoles quinoline, 2-vinyl-4-methyl-2-
Figure BDA00003276409000053
Azoles quinoline, 2-vinyl-5-methyl-2- Azoles quinoline, 2-isopropenyl-2-
Figure BDA00003276409000055
Azoles quinoline, 2-isopropenyl-4-methyl-2- Azoles quinoline, 2-isopropenyl-5-methyl-2-
Figure BDA00003276409000062
Azoles quinoline, 2-isopropenyl-5-ethyl-2-
Figure BDA00003276409000063
Azoles quinoline etc.
As having allylic vinyl monomer, for example can enumerate: acrylic acid allyl ester, ALMA, allyl glycidyl ether etc.
As the vinyl monomer with NCO, for example can enumerate: vinyl isocyanate, pi-allyl isocyanates, (methyl) acrylic acid isocyanates, 2-(methyl) acryloxy ethyl isocyanate, 2-isocyanates ethyl (methyl) acrylate, isopropenyl-α, alpha-alpha-dimethyl methyl-benzyl isocyanates etc.
As the vinyl monomer with oxa-cyclobutyl, for example can enumerate: 3-((methyl) acryloyl-oxy ylmethyl) oxetanes, 3-((methyl) acryloyl-oxy ylmethyl)-2-trifluoromethyl oxetanes, 3-((methyl) acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 2-((methyl) acryloyl-oxy ylmethyl) oxetanes, 2-((methyl) acryloyl-oxy ylmethyl)-4-trifluoromethyl oxetanes etc.
As the vinyl monomer with alkoxysilane group, can enumerate: vinyltrimethoxy silane, vinyltriethoxysilane, methacryloxypropyl methyl dimethoxysilane, methacryloxypropyl trimethoxy silane, methacryloxypropyl methyldiethoxysilane, methacryloxypropyl triethoxysilane, 3-methacryloxy triethoxysilane etc.
In whole polymerized units of adhesive, the ratio that contains of polymerized unit with vinyl monomer of heat cross-linking group is preferably 0.1～10 quality %, more preferably 0.3～7 quality %, be preferably 0.5～5 quality % especially.If have in whole polymerized units of adhesive the heat cross-linking group vinyl monomer polymerized unit contain ratio in above-mentioned scope, then the reactivity with non-conductive organic granular described later improves the dispersion stabilization excellence of non-conductive organic granular in the perforated membrane slurry.And the caking property of adhesive improves, and can suppress non-conductive organic granular and break away from (powder falls) from perforated membrane.
In the present invention, preferred adhesive further contains the polymerized unit of (methyl) acrylate monomer.By making adhesive contain the polymerized unit of (methyl) acrylate monomer, adhesive can not demonstrate the swellability of the appropriateness in electrolyte in the electrolyte stripping of secondary cell, therefore, can keep the conductibility of lithium ion well.Its result can improve the cycle characteristics of secondary cell.
In whole polymerized units of adhesive, the ratio that contains of the polymerized unit of (methyl) acrylate monomer is preferably 50～98 quality %, and more preferably 60～97.5 quality % are preferably 65～95 quality % especially.Polymerized unit by (methyl) acrylate monomer in the whole polymerized units that make adhesive contain ratio in above-mentioned scope, can moderately keep the motility of polymer, improve the flexibility of dispersion stabilization and the perforated membrane of non-conductive organic granular.In addition, 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, because can stripping at electrolyte, can demonstrate the conductibility of lithium ion by the appropriate swelling in electrolyte, and, in the dispersion of non-conductive organic granular, be difficult for the cross-linked cohesion that generation is caused by polymer, therefore preferred alkyl carbon atoms number with non-carbonyl oxygen atom bonding is (methyl) ethyl acrylate of 2～13, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate wherein more preferably is (methyl) n-butyl acrylate of 4～10 with the alkyl carbon atoms number of non-carbonyl oxygen atom bonding, (methyl) 2-EHA.
In addition, in the present invention, preferred adhesive further contains α, the polymerized unit of alpha, beta-unsaturated nitriles monomer.By making adhesive contain α, the polymerized unit of alpha, beta-unsaturated nitriles monomer can improve the intensity of adhesive.
In whole polymerized units of adhesive, α, the ratio that contains of the polymerized unit of alpha, beta-unsaturated nitriles monomer is preferably 1.0～50 quality %, and more preferably 2.5～40 quality % are preferably 5～35 quality % especially.By α in the whole polymerized units that make adhesive, the polymerized unit of alpha, beta-unsaturated nitriles monomer contain ratio in above-mentioned scope, the motility that can moderately keep polymer in the perforated membrane slurry improves the flexibility of dispersion stabilization and the perforated membrane of non-conductive organic granular.In addition, can improve the cycle characteristics of secondary cell.
As α, the alpha, beta-unsaturated nitriles monomer can be enumerated: acrylonitrile or methacrylonitrile.
In addition, with regard to being used for adhesive of the present invention, except above-mentioned polymerized unit (namely, have the polymerized unit of the vinyl monomer of heat cross-linking group, polymerized unit and the α of (methyl) acrylate monomer, the polymerized unit of alpha, beta-unsaturated nitriles monomer) in addition, preferably also contain can with other polymerized unit of their copolymerization.The ratio that contains of other polymerized unit is preferably 0.1～10 quality % in whole polymerized units of adhesive, more preferably 0.1～5 quality %.If in whole polymerized units of adhesive other polymerized unit contain ratio in above-mentioned scope, the dispersiveness of non-conductive organic granular in the perforated membrane slurry then can not take place to be reduced, can be formed uniformly perforated membrane.
As other polymerized unit, can enumerate: styrene 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;
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 vinyl unsaturated carboxylic acid;
Maleic acid, fumaric acid, itaconic acid, citraconic acid, dimethyl maleic acid, phenyl maleic acid, chloromaleic acid, dichloromaleic acid, fluoro maleic acid, and maleate etc. have vinyl unsaturated carboxylic acid and the derivative thereof of dicarboxylic acids;
Olefines such as ethene, propylene; Dienes such as butadiene, isoprene monomer;
Halogen atom such as vinyl chloride, vinylidene chloride monomer;
Vinyl esters such as vinyl acetate, 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 vinyl compound of heterocycle;
Amide-type such as acrylamide, Methacrylamide monomer etc.
Need to prove, can only contain a kind of other polymerized unit in the adhesive, also can contain other polymerized unit more than 2 kinds with the arbitrary ratio combination.
Be used for using under the state of the dispersion liquid that adhesive of the present invention forms being scattered in decentralized medium (water or organic solvent), or use under the state of the solution that forms being dissolved in decentralized medium (water or organic solvent) (below, also they are referred to as " adhesive dispersion liquid ".)。In the present invention, consider from environment aspect excellence, the fast viewpoint of rate of drying, preferably make water as decentralized medium.In addition, under the situation as decentralized medium with an organic solvent, can use N-methyl pyrrolidone organic solvents such as (NMP).
Be scattered in graininess under the situation of decentralized medium at adhesive, the average grain diameter (dispersion particle diameter) of the adhesive that disperses with graininess is preferably 50～500nm, and more preferably 70～400nm most preferably is 100～250nm.If the average grain diameter of adhesive is above-mentioned scope, it is good that the intensity of the second electrode that then obtains and flexibility become.
Be scattered in graininess under the situation of decentralized medium at adhesive, the solid component concentration of dispersion liquid is generally 15～70 quality %, is preferably 20～65 quality %, more preferably 30～60 quality %.If solid component concentration is above-mentioned scope, the operability when then making the perforated membrane slurry is good.
The glass transition temperature (Tg) that is used for adhesive of the present invention is preferably-50～25 ℃, more preferably-45～15 ℃, is preferably-40～5 ℃ especially.Tg by making adhesive is in 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 uses this perforated membrane.Need to prove that the glass transition temperature of adhesive can be by adjusting various set of monomers are incompatible.
Manufacture method as the polymer that is used for adhesive of the present invention is not particularly limited, and can use any means in solution polymerization process, suspension polymerization, mass polymerization, the emulsion polymerization etc.As polymerization reaction, also can adopt any 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, t-butylperoxy pivarate, 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 adhesive of the present invention preferably in the manufacturing process of adhesive, remove operation and the adhesive that obtains through the granular metal of removing granular metal contained in the adhesive dispersion liquid.Be below the 10ppm by the content that makes granular metal composition contained in the adhesive, can prevent from the perforated membrane slurry between polymer taking place along with the process of time metal ion crosslinked, and then can prevent that viscosity from rising.In addition, the dissolving in secondary cell generation internal short-circuit and when charging, to separate out the hidden danger that the self discharge that causes increases few, and the cycle characteristics of battery and fail safe improve.
Removing the method for removing granular metal ingredient in the operation from the adhesive dispersion liquid for above-mentioned granular metal is not particularly limited.For example can enumerate: the method by utilizing filter to filter to remove, 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, so the method for preferably removing by magnetic force.As the method for removing by magnetic force, just be not particularly limited so long as can remove the method for metal ingredient, if consider productivity and remove efficient, then preferably remove by configuration magnetic filter in the manufacturing line of adhesive.
In the manufacturing process that is used for adhesive of the present invention, employed dispersant can be employed dispersant in common synthesizing in the above-mentioned polymerization, as concrete example, can illustration: benzene sulfonates such as neopelex, dodecylphenyl ether sulfonic acid sodium; Alkyl sulfate such as NaLS, sodium tetradecyl sulfate; Sulfosuccinates such as dioctyl sodium sulphosuccinate, dihexyl sodium sulfosuccinate; Soaps such as laurate acid sodium; Ethoxy sulfates such as polyoxyethylene lauryl ether sodium sulfate salt, polyoxyethylene nonylplenyl ether sodium sulfate salt; Paraffin sulfonate; The alkyl ether phosphate sodium salt; Non-ionic emulsifiers such as polyoxyethylene nonylplenyl ether, polyoxyethylene sorbitol acid anhydride Lauryl Ester, polyox-yethylene-polyoxypropylene block copolymer; Gelatin, maleic anhydride-styrene copolymers, PVP, Sodium Polyacrylate, the degree of polymerization are more than 700 and water soluble polymer such as the polyvinyl alcohol of saponification degree more than 75% etc., and these may be used alone, or two or more kinds may be used in combination.Wherein, benzene sulfonates such as preferred neopelex, dodecylphenyl ether sulfonic acid sodium; Alkyl sulfate such as NaLS, sodium tetradecyl sulfate is considered from the aspect of oxidative resistance excellence, benzene sulfonates such as further preferred neopelex, dodecylphenyl ether sulfonic acid sodium.The addition of dispersant can at random be set, and with respect to monomer total amount 100 mass parts, is generally about 0.01～10 mass parts.
PH when being used for adhesive of the present invention and being scattered in decentralized medium is preferably 5～13, and more preferably 5～12, most preferably be 10～12.Be above-mentioned scope by the pH that makes adhesive, the storage stability of adhesive improves, and then mechanical stability improves.
The pH conditioning agent of adjusting the pH of adhesive can illustration: alkaline earth oxides such as alkali metal hydroxides such as lithium hydroxide, NaOH, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, aluminium hydroxide etc. belong to the hydroxide such as hydroxide of the metal of group III A in the long period table (the 13rd family of the periodic table of elements); Carbonate such as alkaline earth metal carbonates such as alkali carbonate such as sodium carbonate, potash, magnesium carbonate etc.; As organic amine, can enumerate: alkyl amines such as ethylamine, diethylamine, propyl group amine; Alcaminess such as single carbinolamine, monoethanolamine, single Propanolamine; Ammonias such as ammoniacal liquor etc.Wherein, consider preferred alkali metal hydroxide, preferred especially NaOH, potassium hydroxide, lithium hydroxide from the viewpoint of caking property and operability.
The ratio that contains of adhesive is preferably 0.5～20 quality % among the per 100 quality % of the total solid composition of perforated membrane slurry, and more preferably 0.5～10 quality % is preferably 1～5 quality % especially.Contain ratio in above-mentioned scope by adhesive among the per 100 quality % of the total solid composition that makes the perforated membrane slurry, can prevent that non-conductive organic granular described later breaks away from (powder falls) from perforated membrane of the present invention, make the flexibility of perforated membrane and use the cycle characteristics of the secondary cell of this perforated membrane to improve.
(non-conductive organic granular)
Be used for non-conductive organic granular of the present invention have can with the crosslinked functional group of the heat cross-linking group of above-mentioned adhesive.In the present invention, by use have can with the non-conductive organic granular of the crosslinked functional group of above-mentioned heat cross-linking group, can improve with above-mentioned adhesive in the reactivity of heat cross-linking group, therefore can improve the dispersiveness of non-conductive organic granular in the perforated membrane slurry.
Be used for non-conductive organic granular of the present invention, can be preferably hydrophilic radical with the crosslinked functional group of heat cross-linking group, specifically can enumerate: carboxyl, sulfonic group, hydroxyl, phosphate etc.Wherein and since with adhesive in heat cross-linking group reactive high, non-conductive organic granular when making the perforated membrane slurry dispersed high, therefore preferred sulfonic group or phosphate, most preferably sulfonic group.By when making non-conductive organic granular, use have can with the monomer of the crosslinked functional group of heat cross-linking group, can in non-conductive organic granular, import this functional group.
As the monomer with carboxyl, can enumerate: the acid anhydrides of monocarboxylic acid, dicarboxylic acids, dicarboxylic acids 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, dichloromaleic acid, and fluoro maleic acid etc.
As the acid anhydrides of dicarboxylic acids, 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 ester in the ninth of the ten Heavenly Stems, maleic acid ester in the last of the ten Heavenly stems, maleic acid dodecyl ester, maleic acid stearyl, and maleate such as maleic acid fluoroalkyl.
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-allyloxy-2-hydroxy-propanesulfonic acid etc.
As the monomer with 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 the ester class that forms of (methyl) acrylic acid; 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; Polyoxyalkylene glycol (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 with phosphate, can enumerate: phosphoric acid-2-(methyl) acryloxy ethyl ester, phosphoric acid methyl-2-(methyl) acryloxy ethyl ester, phosphoric acid ethyl-(methyl) acryloxy ethyl ester etc.
Preferably with respect to non-conductive organic granular, the content of the functional group in the non-conductive organic granular is 0.008～0.240mmol/g, more preferably 0.014～0.14mmol/g.By making amount of functional groups in the non-conductive organic granular in above-mentioned scope, can keep the motility of the functional group in the non-conductive organic granular fully, therefore can improve the reactivity with adhesive.Its result can improve the porous film strength.
Non-conductive organic granular preferably further contains the polymerized unit of divinylbenzene.In the total monomer weight in non-conductive organic granular, the ratio that contains of the polymerized unit of divinylbenzene is preferably 20～80 quality %, and more preferably 25～70 quality % are preferably 30～60 quality % especially.By making the polymerized unit that contains divinylbenzene in the non-conductive organic granular, the crosslink density of conductivity organic granular uprises, and therefore, the thermal endurance of non-conductive organic granular improves, and the reliability of gained secondary cell perforated membrane also improves.
Non-conductive organic granular preferably further contains the polymerized unit of vinyl xylene, ethyl vinyl benzene.In the total monomer weight in non-conductive organic granular, the ratio that contains of the polymerized unit of vinyl xylene, ethyl vinyl benzene is preferably 3.2～48 quality %, more preferably 10～40 quality %.By making the polymerized unit that contains vinyl xylene, ethyl vinyl benzene in the non-conductive organic granular, become well with the caking property of above-mentioned adhesive, can prevent that non-conductive organic granular breaks away from (powder falls) from the secondary cell perforated membrane.In addition, the flexibility of gained secondary cell perforated membrane becomes good.And then, make under the situation of electrode for secondary battery at this secondary cell perforated membrane of electrode superimposed layer, can also prevent the disengaging (powder falls) of electrode active material.Its result uses the secondary cell of this secondary cell perforated membrane to demonstrate excellent cycle characteristics.
The content of the polymerized unit of the polymerized unit of contained divinylbenzene and vinyl xylene, ethyl vinyl benzene is preferably 1.0～5.25 than (divinylbenzene/vinyl xylene, ethyl vinyl benzene) in the non-conductive organic granular, and more preferably 1.25～5.00, be preferably 1.25～4.75 especially.The content of the polymerized unit by making divinylbenzene contained in the non-conductive organic granular and the polymerized unit of vinyl xylene, ethyl vinyl benzene is than being above-mentioned scope, and the crosslink density of non-conductive organic granular uprises, and therefore, the thermal endurance of non-conductive organic granular improves.Its result, the flexibility of gained secondary cell perforated membrane and intensity improve.In addition, can prevent that non-conductive organic granular breaks away from (powder falls) from the secondary cell perforated membrane, simultaneously, under the situation of using this perforated membrane making electrode for secondary battery, can prevent the disengaging (powder falls) of electrode active material, therefore, use the secondary cell of this perforated membrane to demonstrate excellent cycle characteristics.
Except above-mentioned 2 kinds of polymerized units, can also contain any polymerized unit in the non-conductive organic granular.As the monomer that constitutes any polymerized unit (monomer arbitrarily), can enumerate: polynary (methyl) acrylate compounds, aromatic series mono-vinyl compound, acrylonitrile compound, (methyl) acrylate monomer, conjugate diene monomer, vinyl esters compound, alpha-olefin compound, cationic monomer, contain epoxy radicals monomer, amide-containing monomer.Can contain these monomers more than 2 kinds in the non-conductive organic granular.
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 acrylonitrile compound, can enumerate: acrylonitrile, methacrylonitrile etc.
As acrylate monomer, can enumerate: butyl acrylate, acrylic acid 2-ethylhexyl ethyl ester, acrylic acid N, N '-dimethylamino ethyl ester etc.
As methacrylate monomer, can enumerate: butyl methacrylate, methacrylic acid 2-Octyl Nitrite, methyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid N, N '-dimethylamino ethyl ester etc.
As conjugate diene monomer, can enumerate: butadiene, isoprene etc.
As the vinyl esters compound, can enumerate: vinyl acetate etc.
As the alpha-olefin compound, can enumerate: 4-methyl-1-pentene etc.
As cationic monomer, can enumerate: (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid dimethylamino propyl ester etc.
As containing the epoxy radicals monomer, can enumerate: glycidyl acrylate, glycidyl methacrylate etc.
As the amide-containing monomer, can enumerate: acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide etc.
Above-mentioned any monomer can use wantonly a kind or will be used in combination more than 2 kinds separately.In above-mentioned any monomer, particularly from considering optimization styrene, methyl methacrylate or their combination with reactive viewpoint of divinylbenzene and vinyl xylene, ethyl vinyl benzene.
In the total monomer weight in non-conductive organic granular, the ratio that contains of polymerized unit is preferably 3～80 quality % arbitrarily, and more preferably 4～70 quality % are preferably 5～60 quality % especially.Containing under styrene and/or the methyl methacrylate situation as any monomer, be benchmark with the monomer total amount that constitutes non-conductive organic granular particularly, it preferably contains ratio is 4.5～76.5 quality %.Containing under the two the situation of styrene and methyl methacrylate, preferably their total amount is in this scope.The ratio that contains by making styrene and/or methyl methacrylate is below the 76.5 quality %, can improve the thermal endurance of non-conductive organic granular, therefore, can improve the thermal endurance of perforated membrane, and then can reduce the generation of battery short circuit under the high temperature.On the other hand, be more than the 4.5 quality % by the ratio that contains that makes styrene and/or methyl methacrylate, can prevent that the dispersiveness of non-conductive organic granular from reducing, can improve the porous film strength, and, can also obtain film uniformity.
(manufacture method of non-conductive organic granular)
The manufacture method of non-conductive organic granular is not particularly limited, can enumerate following method: will constitute the above-mentioned monomer of non-conductive organic granular and other any composition of using as required is dissolved or dispersed in the decentralized medium, and utilize emulsion polymerization or soap-free polymerization method in this dispersion liquid, to 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 organic granular 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 organic granular (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 organic granular to form seeding polymerization composition granule A, use other monomer of this seeding polymerization composition granule A and the non-conductive organic granular of formation to form the seeding polymerization composition granule B with bigger particle diameter, then, use remaining monomer of this seeding polymerization composition granule B and the non-conductive organic granular of formation and other any composition that uses as required to form the non-conductive organic granular with bigger particle diameter.Like this, form the seeding polymerization composition granule by the reaction by 2 stages, further form non-conductive organic granular then, have and stably to obtain the particle diameter expected and the advantage of average circularity.At this moment, can when forming seeding polymerization composition granule A and seeding polymerization composition granule B, use with partly or entirely (being preferably all) of monomer of the crosslinked functional group of heat cross-linking group constituting having in the monomer of non-conductive organic granular, can guarantee the stability of particle, so preferred.In addition, at this moment, use the monomer that is used to form seeding polymerization composition granule A as the styrene conduct of any monomer, when forming seeding polymerization composition granule B and non-conductive organic granular, can guarantee the absorbability of monomer in the seeding polymerization composition granule, so preferred.
Owing to also comprise the aforesaid situation that a plurality of stages carry out polymerization that is divided into, therefore, constitute the monomer of non-conductive organic granular when polymerization, also can not form the state that its whole monomers become mixture.Be divided under the situation that a plurality of stages carry out in polymerization, in the non-conductive organic granular that finally obtains, preferably satisfy the ratio of components of the monomer of the above-mentioned non-conductive organic granular of formation from the composition of the monomer of the polymerized unit that constitutes non-conductive organic granular.
As employed medium in the polymerization of the monomer that constitutes non-conductive organic granular, can enumerate: water, organic solvent and their mixture.As organic solvent, can use for radical polymerization to be combined into nonactive and can not to hinder the solvent of monomer polymerization.As the concrete example of organic solvent, can enumerate: ketones such as ester class, cyclohexanone such as alcohols such as methyl alcohol, ethanol, propyl alcohol, cyclohexanol, octanol, dibatyl phithalate, dioctyl phthalate, and their mixture.Can preferably make aqueous mediums such as water carry out emulsion polymerisation as polymerization as decentralized medium.
When seeding polymerization composition granule and monomer were reacted, the ratio of their amount was preferably 2～19 mass parts in the use amount of monomer with respect to seeding polymerization composition granule 1 mass parts, more preferably 3～16 mass parts, more preferably 4～12 mass parts.Be more than 2 mass parts by making monomer with respect to the use amount of seeding polymerization composition granule 1 mass parts, can improve mechanical strength and the thermal endurance of the non-conductive organic granular that obtains.In addition, be below 19 mass parts by making monomer with respect to the use amount of seeding polymerization composition granule 1 mass parts, can make monomer be absorbed in the seeding polymerization composition granule 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 the particle diameter of non-conductive organic granular well, therefore, can prevent from having the generation of big particle that wide particle diameter distributes and a large amount of molecule.
As the concrete operations of polymerization, while have with respect to the water-borne dispersions of seeding polymerization composition granule once drop into monomer method, carry out the method that monomer is added in polymerization in batches or continuously.Preferably polymerization be initiated and the seeding polymerization composition granule in produce in fact and make before crosslinked the seeding polymerization composition granule absorb monomer.
If after the mid-term of polymerization, add monomer, then do not absorbed by the seeding polymerization composition granule owing to monomer, therefore may cause a large amount of generations of molecule and make the polymerization stability variation, can't keep polymerization reaction.Therefore, preferably with respect to the seeding polymerization composition granule, before causing, polymerization adds whole monomers or the interpolation of the whole monomers of end before polymerisation conversion reaches about 30%.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 organic granular, can also 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, as water miscible radical polymerization initiator, can enumerate: potassium peroxydisulfate, sodium peroxydisulfate, cumene hydroperoxide, hydrogen peroxide or the redox series initiators that is combined to form by reducing agents such as above-mentioned water soluble starter or oil-soluble initiator described later and sodium hydrogensulfites.In addition, as oil-soluble radical polymerization initiator, can enumerate: benzoyl peroxide, α, α '-azodiisobutyronitrile, peroxide-2-ethyl hexanoic acid tert-butyl, 3,5,5-trimethyl acetyl base peroxide etc.In the oil-soluble radical polymerization initiator, can preferably use peroxide-2-ethyl hexanoic acid tert-butyl.Need to prove, 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.In addition, also can be used in combination nonionic surface active agent such as polyoxyethylene nonylplenyl ether, polyethyleneglycol hard acid esters, sorbitan list hard acid esters.As preferred suspension protective agent, can enumerate: polyvinyl alcohol, carboxymethyl cellulose, Sodium Polyacrylate or micro mist inorganic compound etc.
(proterties of non-conductive organic granular)
Be used for that being shaped as of non-conductive organic granular of the present invention is 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 organic granular, also can use porous particles.The ratio that contains of non-conductive organic granular is preferably 70～97 quality % among the per 100 quality % of the total solid composition of perforated membrane slurry, and more preferably 80～95 quality % are preferably 85～95 quality % especially.The ratio that contains by non-conductive organic granular among the per 100 quality % of the total solid composition that makes the perforated membrane slurry is above-mentioned scope, can obtain showing the perforated membrane of high thermal stability.And the non-conductive organic granular that can be inhibited breaks away from (powder falls) and shows high-intensity perforated membrane from 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, improving the reliability of electrode for secondary battery described later and secondary battery separator, preferred non-conductive organic granular has high-fire resistance.Particularly, under blanket of nitrogen during with the heating of 10 ℃/minute of programming rates, the temperature that the loss of weight ratio of non-conductive organic granular reaches 10 quality % is preferably more than 250 ℃, more preferably more than 300 ℃, is preferably especially more than 360 ℃ by the thermobalance analysis.On the other hand, the upper limit of this temperature is not particularly limited, can be for for example below 450 ℃.
In the present invention, as non-conductive organic granular, preferably use the content of metal impurities to be the non-conductive organic granular below the 100ppm.If use the non-conductive organic granular 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, its result, the porousness of perforated membrane reduces.Therefore, may cause using multiplying power property (output characteristic) variation of the secondary cell of this perforated membrane.As above-mentioned metal, especially, least preferred Ca, Co, Cu, Fe, Mg, Ni, Zn and the Cr etc. of containing.Therefore, as the tenor in the non-conductive organic granular, in the total amount of these metal ions, be preferably below the 100ppm, more preferably below the 50ppm.Above-mentioned content is more few, more is difficult for causing the deterioration of battery behavior.Here described " metal impurities " refer to metal simple-substance or the metal ion beyond the non-conductive organic granular.The content of the metal impurities in the non-conductive organic granular can use ICP (inductively coupled plasma (Inductively Coupled Plasma)) to measure.
The average grain diameter that is used for non-conductive organic granular 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 above-mentioned scope by the average grain diameter that makes non-conductive organic granular, control the dispersity of perforated membrane slurry easily, therefore, produce the perforated membrane with given thickness of homogeneous easily.In addition, can suppress that particles filled rate uprises in the perforated membrane, therefore, the ionic conductivity that can suppress in the perforated membrane reduces, thereby 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 easy degree of then disperseing, being coated with, the controlled excellence in space are preferred especially.Average grain diameter can be obtained as follows: carry out electron microscope observation, for the particle more than 100, with the longest edge of its particle image be made as a, minor face is made as b, calculates (a+b)/2, obtains average grain diameter by its mean value.
The average circularity that is used for non-conductive organic granular 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 above-mentioned scope by the average circularity that makes non-conductive organic granular, can moderately keep non-conductive organic granular contact area each other, therefore, can improve porous film strength and thermal endurance.Its result can improve the reliability of the secondary cell that uses this perforated membrane.
In addition, with regard to being used for the BET specific area of non-conductive organic granular of the present invention, consider from the viewpoint of the cohesion that suppresses non-conductive organic granular and the flowability of optimizing the perforated membrane slurry, particularly, be preferably 0.9～200m 2/ g, more preferably 1.5～150m 2/ g.
The particle diameter of non-conductive organic granular distributes and is preferably 1.00～1.4, and more preferably 1.00～1.3, be preferably 1.00～1.2 especially.Be distributed as above-mentioned scope by the particle diameter that makes non-conductive organic granular, can make the given space of maintenance between non-conductive organic granular, therefore, can suppress in the secondary cell of the present invention to be obstructed and to cause resistance to increase owing to the movement of lithium.Need to prove, the particle diameter of non-conductive organic granular distributes can be after the laser diffraction refraction particle size distribution device (LS230) that uses Beckman Co., Ltd. to make carry out particle size determination, is obtained by the ratio V/N of the volume average particle size V that obtains and number average bead diameter N.
(solvent)
Solvent as being used for the perforated membrane slurry can make any solvent in water and the organic solvent.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, methylethylketone, 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; 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 can be with being mixed and made into mixed solvent more than 2 kinds and using in them.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 (adhesive, non-conductive organic granular and solvent), can also further contain any composition in the perforated membrane slurry.As this any composition, 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 compositions only otherwise 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.The ratio that contains of inorganic particle is below the 20 quality % among the per 100 quality % of the total solid composition of perforated membrane slurry, more preferably below the 10 quality %.If the ratio that contains of inorganic particle is this scope, then can obtain the high perforated membrane of intensity.
As dispersant, but illustration anionic property compound, cationic compound, nonionic compound, macromolecular compound.Dispersant can be selected according to the non-conductive organic granular that uses.Among the per 100 quality % of the total solid composition of perforated membrane slurry dispersant contain ratio preferably in the scope that can not impact battery behavior, be specially 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: surfactants such as alkyls surfactant, silicone surfactant, fluorine class surfactant, metal species surfactant.Among the per 100 quality % of the total solid composition of perforated membrane slurry surfactant contain ratio preferably in the scope that can not impact battery behavior, be specially below the 10 quality %.By mixing above-mentioned surfactant, produce in the time of can preventing from being coated on perforated membrane slurry of the present invention on the given basis material and repel (は じ I), the flatness of perforated membrane is improved.
As antioxidant, can enumerate: phenolic compound, hydroquinone compound, organic phosphorus compound, sulphur compound, phenylenediamine compound, polymer-type phenolic compound etc.The polymer-type phenolic compound is the polymer that has the phenol structure in molecule, and can preferably use weight average molecular weight is 200～1000, preferred 600～700 polymer-type phenolic compound.Among the per 100 quality % of the total solid composition of perforated membrane slurry antioxidant contain ratio preferably in the scope that can not impact battery behavior, be specially 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.The ratio that contains of the binding agent among the per 100 quality % of the total solid composition of perforated membrane slurry 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 and organic dividing plate is good.
As tackifier, can enumerate: cellulosic polymer and their ammonium salt and alkali metal salts such as carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose; (modification) poly-(methyl) acrylic acid and their 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.Among the per 100 quality % of the total solid composition of perforated membrane slurry tackifier contain ratio preferably in the scope that can not impact battery behavior, be specially 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 and 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, can use metallic soap class, polysiloxane-based, polyethers, higher alcohols, perfluoroalkyl class etc.Among the per 100 quality % of the total solid composition of perforated membrane slurry defoamer contain ratio preferably in the scope that can not impact battery behavior, be specially below the 10 quality %.By mixing defoamer, can shorten the froth breaking operation of adhesive.
Electrolysis additive can use in the electrode slurry described later and electrolyte in employed vinylene carbonate etc.Among the per 100 quality % of the total solid composition of perforated membrane slurry electrolysis additive contain ratio preferably in the scope that can not impact battery behavior, be specially below the 10 quality %.By the mixed electrolytic solution additive, the cycle life excellence of battery.
In addition, can enumerate: nanoparticles such as aerosil, 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.
The summation that contains ratio of above-mentioned composition arbitrarily is preferably below the 40 quality % among the per 100 quality % of the total solid composition of perforated membrane slurry, more preferably below the 20 quality %.But, under the situation of the summation less than 100 quality % of above-mentioned adhesive, non-conductive organic granular and any composition (wherein, not comprising binding agent), can by will as the binding agent of any composition contain the suitable increment of ratio, obtain composition.
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 %.
The composition of composition for volatilizing by drying process beyond the solid constituent except above-mentioned solvent, for example also comprises in the preparation of adhesive and non-conductive organic granular 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 any one-tenth that mixes above-mentioned adhesive, non-conductive organic granular, solvent and add as required.In the present invention, by using mentioned component (adhesive, non-conductive organic granular, solvent and any composition that adds as required), no matter how are mixed method and order by merging, all can obtain the perforated membrane slurry that high degree of dispersion has non-conductive particle.Mixing arrangement can use the mixing arrangement identical with the mixing arrangement of the manufacturing that is used for above-mentioned adhesive.Wherein, preferred especially use can apply ball mill, roller mill, the contour dispersal device of filling mixer (Fill-mix, Off ィ Le ミ ッ Network ス) that high dispersive is sheared.
Consider that from the viewpoint of even screening characteristics, slurry ageing stability the viscosity of perforated membrane slurry is preferably 10～10,000mPas, more preferably 50～500mPas.Value when above-mentioned viscosity is measured under 25 ℃, the condition of rotating speed 60rpm for using Brookfield viscometer.
Can be preferably 0.2～3 with respect to the weight ratio of the heat cross-linking group in the adhesive (can with the crosslinked functional group/heat cross-linking group of this heat cross-linking group) with the crosslinked functional group of heat cross-linking group in the non-conductive organic granular in the perforated membrane slurry, more preferably 0.3～3, be preferably 0.3～2 especially.If (can with the crosslinked functional group/heat cross-linking group of this heat cross-linking group) be above-mentioned scope this weight ratio, then can prevent the gelation of perforated membrane slurry, makes the screening characteristics of perforated membrane slurry good, therefore, and the flexibility of perforated membrane and intensity raising.
(2) secondary cell perforated membrane
Secondary cell perforated membrane of the present invention (following also note is made " perforated membrane ") forms above-mentioned secondary cell perforated membrane slurry membranaceous and carries out drying and forms.
In addition, perforated membrane of the present invention adhesive that the polymerized unit that comprises the vinyl monomer with heat cross-linking group forms and have can and the non-conductive organic granular of the crosslinked functional group of this heat cross-linking group between have cross-linked structure.Described cross-linked structure is that adhesive and non-conductive organic granular carry out the molecular structure that bonding forms by chemical bond.
Perforated membrane is stacked on and uses on organic dividing plate, the electrode or use as organic dividing plate itself.
The manufacture method of＜secondary cell perforated membrane 〉
As the method for making perforated membrane of the present invention, can enumerate: the perforated membrane slurry that (I) will contain above-mentioned adhesive, non-conductive organic granular, solvent and any composition is coated on the given basis material (positive pole, negative pole or organic dividing plate), carries out dry method then; (II) after the perforated membrane slurry that will contain above-mentioned adhesive, non-conductive organic granular, solvent and any composition is immersed in the basis material (anodal, negative pole or organic dividing plate), it is carried out dry method; (III) the perforated membrane slurry that will contain above-mentioned adhesive, non-conductive organic granular, solvent and any composition is coated on and carries out film forming on the stripping film, and with the perforated membrane transfer printing that the obtains method on given basis material (anodal, negative pole or organic dividing plate).Wherein, (I) the perforated membrane slurry is coated on the thickness that the method for carrying out drying on the basis material (positive pole, negative pole or organic dividing plate) is then controlled perforated membrane easily, so most preferably.
Perforated membrane of the present invention can be by the method manufacturing of above-mentioned (I)～(III), below, its concrete manufacture method is described.
In the method for (I), by the perforated membrane slurry being coated on given basis material (positive pole, negative pole or organic dividing plate) upward and carrying out drying and make perforated membrane of the present invention.
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, contrary roller method, direct rolling 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, preferably under the low temperature below 100 ℃, carry out drying.
In the method for (II), by the perforated membrane slurry being impregnated in the basis material (positive pole, negative pole or organic dividing plate) and carrying out drying and make perforated membrane of the present invention.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.
For the perforated membrane that the method by (I)～(III) obtains, also can follow the adaptation of using moulding press, roll squeezer etc. to improve basis material (positive pole, negative pole or organic dividing plate) and perforated membrane by pressurized treatments as required.But 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 suit to set according to purposes or the 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 monomer 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 is preferably used as diaphragm or the dividing plate of electrode active material layer described later especially at the surface filming of basis material (positive pole, negative pole or organic dividing plate).Perforated membrane of the present invention can be in the arbitrary surfaces film forming of positive pole, negative pole or organic dividing plate of secondary cell, also can be in film forming on anodal, negative pole and organic dividing plate whole.
(3) electrode for secondary battery
As secondary cell, can enumerate: lithium rechargeable battery, nickel-hydrogen secondary cell etc.Wherein, to import effect the highest owing to require most to improve fail safe and perforated membrane, so the preferred lithium ion secondary battery, therefore, below the situation that is used for lithium rechargeable battery described.
Electrode for secondary battery of the present invention contains collector body, is attached to this collector body and contains electrode active material and the electrode active material layer of binding agent and be stacked on the lip-deep above-mentioned secondary cell perforated membrane of this electrode active material layer.That is, electrode for secondary battery of the present invention is attached with the electrode active material layer that comprises electrode active material and binding agent for electrode at collector body, and at the surperficial lamination of electrode active material layer above-mentioned secondary cell perforated membrane is arranged.
(electrode active material)
Employed electrode active material in the electrode for lithium ion secondary battery is so long as can voltage reversibly embeds or the active material of removal lithium embedded ion gets final product by applying 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, can 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.Also can be that part element in these compounds is replaced the resulting compound in back.As the positive active material that is constituted by organic compound, also can use for example polyacetylene, poly-to electroconductive polymers such as benzene.For the iron type oxide of poorly conductive, can when carrying out reduction roasting, there be carbon source material by making it, be made into the electrode active material that is covered by material with carbon element and use.In addition, these compounds also can be that the part element is replaced the resulting compound in back.
Positive electrode active material for lithium ion secondary battery also can be above-mentioned inorganic compound and the mixture of organic compound.The particle diameter of positive active material can according to and any constitutive requirements of battery between balance suit to select, but consider from the viewpoint that battery behaviors such as multiplying power property, cycle characteristics improve, 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.
, 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. with electrode active material (negative electrode active material) as lithium ion secondary battery negative pole.In addition, as negative electrode active material, can use metals such as silicon, tin, zinc, manganese, iron, nickel or their alloy, the oxide of above-mentioned metal or alloy, sulfate.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 and give the active material that material forms in the surface attachment conduction.The particle diameter of negative electrode active material can according to and other constitutive requirements of battery between balance 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, also note is made " binding agent for electrode ".)。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.
In addition, can also use following illustrative soft polymer as binding agent for electrode.
Can enumerate:
Acrylic compounds 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 they and the copolymer that can form with the monomer of its copolymerization;
Isobutylene type soft polymer: polyisobutene, butyl rubber, isobutylene-styrene copolymer etc.;
Dienes soft polymer: polybutadiene, polyisoprene, butadiene-styrene random copolymer, isoprene-styrene random copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, butadiene-styrene block copolymer, SBS, isoprene-styrene block copolymer, SIS etc.;
Siliceous soft polymer: dimethyl polysiloxane, diphenyl polysiloxanes, dihydroxy polysiloxanes etc.;
Olefines soft polymer: liquid polyethylene, polypropylene, poly-1-butylene, ethene-alpha-olefin copolymer, propylene-alpha-olefin copolymers, ethylene-propylene-diene copolymer (EPDM), ethylene-propylene-styrol copolymer etc.;
Vinyl-based soft polymer: polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinyl acetate styrene copolymer etc.;
Epoxies soft polymer: poly(ethylene oxide), PPOX, epichlorohydrin rubber etc.;
Fluorine-containing soft polymer: vinylidene class rubber, tetrafluoroethylene-acrylic rubber etc.;
Other soft polymer: natural rubber, polypeptide, protein, polyesters thermoplastic elastomer (TPE), polyvinyl chloride-base thermoplastic elastomer, polyamide-based thermoplastic elastomer (TPE) etc.; Etc..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 making 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, prepare binding agent for electrode 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 rotating speed 60rpm for using Brookfield viscometer.
(additive arbitrarily)
In the present invention, except above-mentioned electrode active material and binding agent for electrode, also can contain conductivity and give additive arbitrarily such as material, reinforcing material in the electrode active material layer.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 reach.By using conductivity to give material, can improve electrode active material electrically contacting each other, be used for can improving the discharge-rate characteristic under the situation of lithium rechargeable battery.With respect to electrode active material 100 mass parts, the use amount that conductivity is given material and reinforcing material is generally 0～20 mass parts, is preferably 1～10 mass parts.In addition, in electrode active material layer, also can contain isothiazoline based compound and chelate compound
Electrode active material layer can make the slurry that contains electrode active material, binding agent for electrode and solvent (below, be also 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 binding agent for electrode is dispersed into granular solvent gets final product the solvent of preferred dissolution binding agent for electrode.If use lysis electrodes with the solvent of binding agent, then binding agent for electrode can be adsorbed in electrode active material and the surface of additive arbitrarily, can make the decentralized stabilization of electrode active material etc. thus.
Solvent as being used for electrode slurry can make any solvent in water and the organic solvent.As organic solvent, can enumerate: annular aliphatic hydro carbons such as pentamethylene, cyclohexane; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; Ketone such as methylethylketone, 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.Can suit to select to use a kind in these solvents or be mixed with two or more under the situation aspect considering rate of drying and environment.
Can further contain the additive that tackifier etc. show various functions in the electrode slurry.As tackifier, can use the polymer that dissolves in solvent 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 also 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 compositions can also contain in electrolyte described later and use.
According to the kind of electrode active material and binding agent for electrode etc., adjust the solvent in the electrode slurry amount, make it reach the viscosity that is suitable for applying and use.Particularly, preferably adjust, make electrode active material, binding agent for electrode and conductivity in electrode slurry give material etc. arbitrarily the concentration of total solid constituent of additive reach 30～90 quality %, 40～80 quality % and using 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, it is microgranular giving with conductivity that material and tackifier mix and make conductivity give dispersion of materials in solvent, add binding agent for electrode, electrode active material then, and then mix, the dispersiveness of slurry is improved, so 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, 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 obtain the electrode of homogeneous.
(collector body)
As long as collector body is considered metal materials such as preference such as 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 from having stable on heating viewpoint.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 sheet collector body about preferred thickness 0.001～0.5mm.For collector body, in order to improve the adhesion strength of electrode active material layer, preferably carry out roughening in advance and handle the back use.As the roughening method, can enumerate: mechanical polishing method, electrobrightening method, chemical polishing etc.In mechanical polishing method, can use adhesion has the polishing agent particle sand paper, grinding stone, diamond dust (emery buff), possess the line brush of steel wire etc. etc.In addition, for adhesion strength and the conductivity that improves electrode active material layer, also 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, then in the heat treated of carrying out more than 120 ℃ more than 1 hour, form electrode active material layer.Method at collector body coating electrode slurry is not particularly limited.For example can enumerate: methods such as scraper rubbing method, infusion process, contrary roller method, direct rolling 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 preferable 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, can produce and be difficult for to obtain high volume capacity or electrode active material layer and peel off easily and be easy to generate bad such problem.In addition, under the situation of using curable polymer, preferably be cured.
With regard to the thickness of electrode active material layer, anodal, negative pole all is generally 5～300 μ m, is preferably 10～250 μ m.
The electrode active material layer surface superimposed layer secondary cell perforated membrane of the present invention of the collector body of electrode for secondary battery of the present invention by being bonded as stratiform at electrode active material layer is made.
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 comprises institute's lamination on organic dividing plate, this organic dividing plate forms.That is, secondary battery separator of the present invention is by forming at the above-mentioned secondary cell perforated membrane of the surperficial superimposed layer of organic dividing plate.
(organic dividing plate)
As the organic dividing plate of lithium rechargeable battery, can use vistanexes such as polyethylene, polypropylene, comprise the known dividing plates such as dividing plate of aromatic polyamide resin.
As being used for organic dividing plate of the present invention, can use and not have electronic conductivity and have ionic conductivity, the patience height of organic solvent, and the multiple aperture plasma membrane that the aperture is fine can be enumerated by for example TPO (polyethylene, polypropylene, polybutene, polyvinyl chloride), and resins such as their mixture or copolymer form 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 form, or the collector body that is formed by TPO fibrage, 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, thereby thickness that can attenuate dividing plate integral body, improve the aspect that active material ratio in the battery improves the capacity of unit volume and consider, preferably the micro-porous film that is formed by polyolefin resin.
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 polyolefin resin of the material that is used as 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, consider from the purpose of giving flexibility, also can be with mixing more than 2 kinds in the above-mentioned polyethylene.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 preferably 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, and 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 TPO, can use public method, for example can from following method, select: polypropylene, polyethylene are melt extruded and film processed 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, make its film forming, 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, the preferred dry method is considered in the aspect that obtains big 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 coat 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 consider with the aspect of the adaptation of above-mentioned perforated membrane from the impregnation height of electrolyte, easy acquisition, preferably coat processing with the macromolecular compound that contains carboxylic acid group, hydroxyl and sulfonic group isopolarity group.
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 (I)～(III) that illustrate 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, at any materials superimposed layer of anodal, negative pole and organic dividing plate above-mentioned secondary cell perforated membrane is arranged.
(electrolyte)
As electrolyte, use the organic electrolyte that the dissolving supporting electrolyte forms in organic solvent.As supporting electrolyte, can 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 high degree of dissociation 6, LiClO 4, CF 3SO 3Li.These also can be used in combination more than two kinds.Then lithium ion conductivity is more high owing to more use the high supporting electrolyte of degree of dissociation, therefore, can regulate lithium ion conductivity according to the kind of supporting electrolyte.
As the organic solvent that is used for electrolyte, just be not particularly limited so long as can dissolve the solvent of supporting electrolyte, 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, methyl-sulfoxide 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 more low then lithium ion conductivity of viscosity of the solvent that uses becomes more high, therefore, can regulate lithium ion conductivity according to solvent types.
As the concrete manufacture method of secondary cell, can enumerate: positive pole and negative pole are carried out across organic dividing plate superimposed, and according to cell shapes with its curl, bending etc. puts into battery case, injects electrolyte and method for sealing in 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, 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 independently perforated membrane be stacked on positive pole, negative pole or organic dividing plate.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 the arbitrary shape in Coin shape, coin shape, sheet type, cylinder type, square, platypelloid type etc.
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 shrinks because being heated, the short circuit between positive pole/negative pole can not take place yet, can keep high security.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, using under the situation of organic dividing plate, also can landfill be formed at the 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.Need to prove 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 organic granular (T10 value) 〉
Under blanket of nitrogen, utilize thermobalance to heat for 10 ℃/minute from 30 ℃ with programming rate, the loss of weight ratio of obtaining non-conductive particle reach the temperature of 10 quality % [℃], as heat resisting temperature.
Flexibility and the mealiness that falls of＜electrode for secondary battery (electrode of band perforated membrane) or secondary battery separator (organic dividing plate of band perforated membrane) 〉
The electrode for secondary battery electrode of perforated membrane (band) or secondary battery separator (organic dividing plate of band perforated membrane) are cut into the rectangle of width 1cm * length 5cm, make test film.Make face-down be placed on desk on opposite with the perforated membrane side of test film, broad ways arranges the stainless steel bar of diameter 1mm with couching on the central authorities (position of end 2.5cm) of length direction, the face opposite with the perforated membrane side.Centered by this stainless steel bar test film crooked 180 being spent and made the porous rete is the outside.10 test films are tested, and the sweep of the porous rete of each test film is observed has flawless or the powder that falls, and judges by following benchmark.Crackle, to peel off powder more few, on the expression electrode active material layer or flexibility and the mealiness that falls of the perforated membrane that forms on organic dividing plate more excellent.
A: in whole 10, all do not find crackle and the powder that falls.
B: find crackle or the powder that falls in 1～3 in 10.
C: find crackle or the powder that falls in 4～6 in 10.
D: find crackle or the powder that falls in 7～9 in 10.
E: whole middle crackle or the powder that falls found in 10.
The amount of moisture of＜secondary cell perforated membrane 〉
Electrode for secondary battery (electrode of band perforated membrane) or secondary battery separator (organic dividing plate of band perforated membrane) are cut into width 10cm * length 10cm, make test film.Test film was placed 24 hours below 25 ℃ of temperature, dew point-60 ℃.Then, use coulometric titration formula moisture meter by the amount of moisture of Ka Er-Fei Xiefa (150 ℃ of JISK-0068 (2001) moisture evaporating method, gasification temperatures) determination test sheet, calculate the amount of moisture of the per unit volume of perforated membrane.The amount of moisture of the per unit volume of perforated membrane is more few, more can not caused by moisture and battery behavior can not take place side reaction in the battery reduce, so preferred.
A: be lower than 1.0mg/cm 3
B:1.0mg/cm 3More than and be lower than 1.5mg/cm 3
C:1.5mg/cm 3More than and be lower than 3.0mg/cm 3
D:3.0mg/cm 3More than
＜metals content impurity 〉
Use inductively coupled plasma ICP Atomic Emission Spectrophotometer device (ICP-AES; SII Nanotechnology company) total content (ppm) to the metal impurities in the non-conductive organic granular (Ca, Co, Cr, Cu, Fe, Mg, Ni, Zn) has carried out quantitative analysis.The content of the metal impurities in the non-conductive organic granular is more few, battery behavior more can not take place reduce, so preferred.
A: be lower than 50ppm
B:50ppm is above and be lower than 100ppm
C:100ppm is above and be lower than 200ppm
More than the D:200ppm
The cycle characteristics of＜secondary cell 〉
About the Coin-shaped battery of Unit 10, in 60 ℃ thermostat, repeat to charge to 4.3V and be discharged to discharging and recharging of 3.0V by the constant current anodizing process of 0.2C, measure discharge capacity.The mean value of Unit 10 as measured value, is calculated the discharge capacity of the 60th circulation with respect to the ratio of the discharge capacity of the 5th circulation with percentage, obtain capability retention, with following benchmark evaluation cycle characteristics.This value is more high, and cycle characteristics is more excellent.
More than the A:90%
B:80% is above and be lower than 90%
C:70% is above and be lower than 80%
D:60% is above and be lower than 70%
E: be lower than 60%
(embodiment 1)
The manufacturing of＜(1) seeding polymerization composition granule A 〉
In possessing 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 〉
In possessing the reactor of mixer, put into 2 parts of the aqueous dispersions of the seeding polymerization composition granule A that operation (1) obtains (in the solid constituent benchmark, namely, weight basis in seeding polymerization composition granule A), 0.2 part of neopelex, 0.5 part of potassium peroxydisulfate, and 100 parts of ion exchange waters, 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 have prepared the dispersion of monomer mixture.The dispersion of this monomer mixture was added in the said mixture continuously through 4 hours, make its polymerization.In the process of the dispersion of interpolation monomer mixture, the temperature maintenance of reaction system is 80 ℃, reacts continuously.After adding end continuously, further continue reaction 3 hours down at 90 ℃.
Obtain the aqueous dispersion of the seeding polymerization composition granule B of average grain diameter 200nm thus.
The manufacturing of the non-conductive organic granular in＜(3) 〉
Then, in possessing the reactor of mixer, put into 10 parts of the aqueous dispersions of the seeding polymerization composition granule B that operation (2) obtains (in the solid constituent benchmark, namely, weight basis in seeding polymerization composition granule B), 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) 88.5 parts, 1.5 parts of 2-acrylamides-2-methyl propane sulfonic acid, 1.0 parts of neopelexes, peroxide-2-ethyl hexanoic acid tert-butyl (day oily corporate system as polymerization initiator, trade name: Perbutyl O) 5 parts, reach 200 parts of ion exchange waters, 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 organic granular of average grain diameter 0.4 μ m.
From the seeding polymerization composition granule form beginning to the heat resisting temperature (T10 value) of the composition that obtains employed monomer (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and 2-acrylamide-2-methyl propane sulfonic acid) till the non-conductive organic granular and non-conductive organic granular, adhesive can be as shown in table 1 with content and the metals content impurity of the crosslinked functional group's (sulfonic group) of heat cross-linking group (epoxy radicals).
The manufacturing of＜(4) adhesive 〉
In possessing the reactor of mixer, put into 0.3 part of 70 parts of ion exchange waters, 0.4 part of neopelex and potassium peroxydisulfate, mix and obtain mixture, be warming up to 60 ℃.
On the other hand, 50 parts of hybrid ionic exchanged waters, 0.8 part of neopelex, 77.7 parts of 2-EHAs, 20 parts of acrylonitrile, 2.3 parts of glycidyl methacrylate obtain monomer mixture in another container.
This monomer mixture was added in the said mixture continuously through 4 hours, make its polymerization.The temperature maintenance of reaction system is 60 ℃ in the interpolation process continuously, reacts.After adding end continuously, further continue reaction 3 hours down at 70 ℃, obtain containing the aqueous dispersions (adhesive aqueous dispersions) of adhesive.
After the adhesive aqueous dispersions that obtains is cooled to 25 ℃, to wherein adding ammoniacal liquor pH is adjusted to 7, then, imports steam and remove unreacted monomer.Then, with respect to 100 parts of the solid constituents of adhesive, add 0.25 part of ethylenediamine tetra-acetic acid immediately, they are mixed, further carry out the adjustment of solid component concentration with ion exchange water on one side, stainless steel woven wire with 200 orders (the about 77 μ m of mesh) filters on one side, the perforated membrane aqueous dispersions of adhesive that obtains average grain diameter 100nm, solid component concentration 40%.
Perforated membrane with the polymerized unit of the vinyl monomer that has the heat cross-linking group in the adhesive (glycidyl methacrylate) contain that ratio is 2.3%, the polymerized unit of (methyl) acrylate monomer contain that ratio is 77.7%, α, the ratio that contains of the polymerized unit of alpha, beta-unsaturated nitriles monomer is 20%.
The manufacturing of＜(5) perforated membrane slurry 〉
Using degree of etherification falling is that 0.8～1.0,1% solution viscosity is that the carboxymethyl cellulose (Daicel1220 processed of Daicel chemical industry Co., Ltd.) of 10～20mPas has prepared 1% aqueous solution as tackifier.
Be that the mode of 83.1:12.3:4.6 in water mix with 1% aqueous solution of the aqueous dispersions of adhesive and carboxymethyl cellulose with the solid constituent weight ratio with the perforated membrane that obtains in the aqueous dispersion of the non-conductive organic granular that obtains in the operation (3), the operation (4), further add the water as solvent, use ball mill to make its dispersion, obtain the perforated membrane slurry.Wherein, making the content of the raw material (total of solid constituent) beyond the water in the perforated membrane slurry is 50 quality %.
The manufacturing that＜(6) are anodal 〉
As adding PVDF as binding agent for electrode (Kynoar, Wu Yu chemistry corporate system, trade name: KF-1100) and make PVDF count 3 parts with solid constituent conversion amount in 95 parts of the LiMn2O4s with spinel structure of positive active material, add 2 parts of acetylene blacks then, 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 the one side of the aluminium foil of thickness 18 μ m with slurry, at 120 ℃ down after dry 3 hours, carry out roll-in and make the positive pole with positive electrode active material layer that gross thickness is 100 μ m.
The manufacturing of＜(7) 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, as 1 part of mixing of solid constituent conversion amount of the SBR (styrene butadiene rubbers, glass transition temperature :-10 ℃) of binding agent for electrode, in this mixture, further mix 1.0 parts of carboxy methyl celluloses, further add the water as solvent, they are mixed the negative pole electrod composition (negative pole slurry) of preparation pulp-like with planetary stirring machine.This negative pole is coated the one side of the Copper Foil of thickness 18 μ m with slurry, at 110 ℃ 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＜(8) 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.Using the line rod is the perforated membrane slurry that obtains in the mode painting process (5) of 5 μ m with dried thickness on a side surface of this organic dividing plate, obtains pulp layer, with pulp layer 50 ℃ dry 10 minutes down, form perforated membrane.Next, form perforated membrane similarly on the opposite side surface of organic dividing plate, obtain having on the two sides organic dividing plate of the band perforated membrane of perforated membrane.
＜(9) 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 (6) is cut into the circle of diameter 13mm, obtains circular positive pole.The negative pole that obtains in the operation (7) is cut into the circle of diameter 14mm, obtains circular negative pole.In addition, organic dividing plate of the band perforated membrane that obtains in the operation (8) is cut into the circle of diameter 18mm, obtains 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.Circular positive pole is with the face of its aluminium foil side mode mounting towards the face of the bottom surface side of outer packaging container, positive electrode active material layer one side towards upside.Circular negative pole is with the face of its negative electrode active material layer one side mode mounting towards the face of organic bulkhead sides of the band perforated membrane of circle, Copper Foil side towards upside.By with this container 105 ℃ of following vacuumizes 24 hours, the crosslinked of adhesive and non-conductive organic fine particles carried out, then the residual moisture in the system is removed.
In container, inject electrolyte in the mode of residual air not, 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, used in the mixed solvent that ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed with EC:DEC=1:2 (volumetric ratios under 20 ℃) the concentration dissolving LiPF with 1 mol 6The solution that forms.
＜(10) are estimated 〉
Cycle characteristics to flexibility, the mealiness that falls and the amount of moisture of organic dividing plate of the band perforated membrane that obtains and the secondary cell that obtains is estimated.The result is as shown in table 1.
(embodiment 2)
The non-conductive organic granular that obtains in operation (1)～(3) of replacement embodiment 1 has used following non-conductive organic granular.In addition, the perforated membrane adhesive that obtains in the operation (4) of replacement embodiment 1 has used following perforated membrane adhesive.Use this non-conductive organic granular and this perforated membrane to make the perforated membrane slurry with adhesive, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜non-conductive organic granular 〉
In possessing the reactor of mixer, put into 10 parts of the aqueous dispersions of the seeding polymerization composition granule B that operation (2) obtains (in the solid constituent benchmark, namely, weight basis in seeding polymerization composition granule B), 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) 89.6 parts, 0.4 part of 2-acrylamide-2-methyl propane sulfonic acid, 1.0 parts of neopelexes, peroxide-2-ethyl hexanoic acid tert-butyl (day oily corporate system as polymerization initiator, trade name: Perbutyl O) 5 parts, reach 200 parts of ion exchange waters, 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 organic granular of average grain diameter 0.4 μ m.
From the seeding polymerization composition granule form beginning to the heat resisting temperature (T10 value) of the composition that obtains employed monomer (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and 2-acrylamide-2-methyl propane sulfonic acid) till the non-conductive organic granular and non-conductive organic granular, adhesive can be as shown in table 1 with content and the metals content impurity of the crosslinked functional group's (sulfonic group) of heat cross-linking group (epoxy radicals).
The manufacturing of＜adhesive 〉
In possessing the reactor of mixer, put into 0.3 part of 70 parts of ion exchange waters, 0.4 part of neopelex and potassium peroxydisulfate, mix and obtain mixture, be warming up to 60 ℃.
On the other hand, 50 parts of hybrid ionic exchanged waters, 0.8 part of neopelex, 78.4 parts of 2-EHAs, 21 parts of acrylonitrile, 0.6 part of glycidyl methacrylate obtain monomer mixture in another container.
This monomer mixture was added in the said mixture continuously through 4 hours, make its polymerization.The temperature maintenance of reaction system is 60 ℃ in the interpolation process continuously, reacts.After adding end continuously, further continue reaction 3 hours down at 70 ℃, obtain containing the aqueous dispersions (adhesive aqueous dispersions) of adhesive.
After the adhesive aqueous dispersions that obtains is cooled to 25 ℃, to wherein adding ammoniacal liquor pH is adjusted to 7, imports steam then and remove unreacted monomer.Then, with respect to 100 parts of the solid constituents of adhesive, add 0.25 part of ethylenediamine tetra-acetic acid immediately, they are mixed, further carry out the adjustment of solid component concentration with ion exchange water on one side, stainless steel woven wire with 200 orders (the about 77 μ m of mesh) filters on one side, the perforated membrane aqueous dispersions of adhesive that obtains average grain diameter 100nm, solid component concentration 40%.
Perforated membrane with the polymerized unit of the vinyl monomer with heat cross-linking group (glycidyl methacrylate) in the adhesive contain that ratio is 0.6%, the polymerized unit of (methyl) acrylate monomer contain that ratio is 78.4%, α, the ratio that contains of the polymerized unit of alpha, beta-unsaturated nitriles monomer is 21%.
(embodiment 3)
The non-conductive organic granular that obtains in operation (1)～(3) of replacement embodiment 1 has used following non-conductive organic granular.In addition, the perforated membrane adhesive that obtains in the operation (4) of replacement embodiment 1 has used following perforated membrane adhesive.Use this non-conductive organic granular and this perforated membrane to make the perforated membrane slurry with adhesive, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜non-conductive organic granular 〉
In possessing the reactor of mixer, put into 10 parts of the aqueous dispersions of the seeding polymerization composition granule B that operation (2) obtains (in the solid constituent benchmark, namely, weight basis in seeding polymerization composition granule B), 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) 87.2 parts, 2.8 parts of 2-acrylamides-2-methyl propane sulfonic acid, 1.0 parts of neopelexes, peroxide-2-ethyl hexanoic acid tert-butyl (day oily corporate system as polymerization initiator, trade name: Perbutyl O) 5 parts, reach 200 parts of ion exchange waters, 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 organic granular of average grain diameter 0.4 μ m.
From the seeding polymerization composition granule form beginning to the heat resisting temperature (T10 value) of the composition that obtains employed monomer (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and 2-acrylamide-2-methyl propane sulfonic acid) till the non-conductive organic granular and non-conductive organic granular, adhesive can be as shown in table 1 with content and the metals content impurity of the crosslinked functional group's (sulfonic group) of heat cross-linking group (epoxy radicals).
The manufacturing of＜adhesive 〉
In possessing the reactor of mixer, put into 0.3 part of 70 parts of ion exchange waters, 0.4 part of neopelex and potassium peroxydisulfate, mix and obtain mixture, be warming up to 60 ℃.
On the other hand, 50 parts of hybrid ionic exchanged waters, 0.8 part of neopelex, 76.5 parts of 2-EHAs, 19 parts of acrylonitrile, 4.5 parts of glycidyl methacrylate obtain monomer mixture in another container.
This monomer mixture was added in the said mixture continuously through 4 hours, make its polymerization.The temperature maintenance of reaction system is 60 ℃ in the interpolation process continuously, reacts.After adding end continuously, further continue reaction 3 hours down at 70 ℃, obtain containing the aqueous dispersions (adhesive aqueous dispersions) of adhesive.
After the adhesive aqueous dispersions that obtains is cooled to 25 ℃, to wherein adding ammoniacal liquor pH is adjusted to 7, imports steam then and remove unreacted monomer.Then, with respect to 100 parts of the solid constituents of adhesive, add 0.25 part of ethylenediamine tetra-acetic acid immediately, they are mixed, further carry out the adjustment of solid component concentration with ion exchange water on one side, stainless steel woven wire with 200 orders (the about 77 μ m of mesh) filters on one side, the perforated membrane aqueous dispersions of adhesive that obtains average grain diameter 100nm, solid component concentration 40%.
Perforated membrane with the polymerized unit of the vinyl monomer with heat cross-linking group (glycidyl methacrylate) in the adhesive contain that ratio is 4.5%, the polymerized unit of (methyl) acrylate monomer contain that ratio is 76.5%, α, the ratio that contains of the polymerized unit of alpha, beta-unsaturated nitriles monomer is 19%.
(embodiment 4)
The perforated membrane adhesive that obtains in the operation (4) of replacement embodiment 1, use following perforated membrane to make the perforated membrane slurry with adhesive, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜adhesive 〉
In possessing the reactor of mixer, put into 0.3 part of 70 parts of ion exchange waters, 0.4 part of neopelex and potassium peroxydisulfate, mix and obtain mixture, be warming up to 60 ℃.
On the other hand, 50 parts of hybrid ionic exchanged waters, 0.8 part of neopelex, 91 parts of 2-EHAs, 7 parts of acrylonitrile, 2 parts of glycidyl methacrylate obtain monomer mixture in another container.
This monomer mixture was added in the said mixture continuously through 4 hours, make its polymerization.The temperature maintenance of reaction system is 60 ℃ in the interpolation process continuously, reacts.After adding end continuously, further continue reaction 3 hours down at 70 ℃, obtain containing the aqueous dispersions (adhesive aqueous dispersions) of adhesive.
After the adhesive aqueous dispersions that obtains is cooled to 25 ℃, to wherein adding ammoniacal liquor pH is adjusted to 7, imports steam then and remove unreacted monomer.Then, with respect to 100 parts of the solid constituents of adhesive, add 0.25 part of ethylenediamine tetra-acetic acid immediately, they are mixed, further carry out the adjustment of solid component concentration with ion exchange water on one side, stainless steel woven wire with 200 orders (the about 77 μ m of mesh) filters on one side, the perforated membrane aqueous dispersions of adhesive that obtains average grain diameter 100nm, solid component concentration 40%.
Perforated membrane with the polymerized unit of the vinyl monomer with heat cross-linking group (glycidyl methacrylate) in the adhesive contain that ratio is 2%, the polymerized unit of (methyl) acrylate monomer contain that ratio is 91%, α, the ratio that contains of the polymerized unit of alpha, beta-unsaturated nitriles monomer is 7%.
(embodiment 5)
The perforated membrane adhesive that obtains in the operation (4) of replacement embodiment 1, use following perforated membrane to make the perforated membrane slurry with adhesive, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜adhesive 〉
In possessing the reactor of mixer, put into 0.3 part of 70 parts of ion exchange waters, 0.4 part of neopelex and potassium peroxydisulfate, mix and obtain mixture, be warming up to 60 ℃.
On the other hand, 50 parts of hybrid ionic exchanged waters, 0.8 part of neopelex, 67 parts of 2-EHAs, 30 parts of acrylonitrile, 3 parts of glycidyl methacrylate obtain monomer mixture in another container.
This monomer mixture was added in the said mixture continuously through 4 hours, make its polymerization.The temperature maintenance of reaction system is 60 ℃ in the interpolation process continuously, reacts.After adding end continuously, further continue reaction 3 hours down at 70 ℃, obtain containing the aqueous dispersions (adhesive aqueous dispersions) of adhesive.
After the adhesive aqueous dispersions that obtains is cooled to 25 ℃, to wherein adding ammoniacal liquor pH is adjusted to 7, imports steam then and remove unreacted monomer.Then, with respect to 100 parts of the solid constituents of adhesive, add 0.25 part of ethylenediamine tetra-acetic acid immediately, they are mixed, further carry out the adjustment of solid component concentration with ion exchange water on one side, stainless steel woven wire with 200 orders (the about 77 μ m of mesh) filters on one side, the perforated membrane aqueous dispersions of adhesive that obtains average grain diameter 100nm, solid component concentration 40%.
Perforated membrane with the polymerized unit of the vinyl monomer with heat cross-linking group (glycidyl methacrylate) in the adhesive contain that ratio is 3%, the polymerized unit of (methyl) acrylate monomer contain that ratio is 67%, α, the ratio that contains of the polymerized unit of alpha, beta-unsaturated nitriles monomer is 30%.
(embodiment 6)
The non-conductive organic granular that obtains in operation (1)～(3) of replacement embodiment 1, use following non-conductive organic granular to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜non-conductive organic granular 〉
In possessing the reactor of mixer, put into 10 parts of the aqueous dispersions of the seeding polymerization composition granule B that operation (2) obtains (in the solid constituent benchmark, namely, weight basis in seeding polymerization composition granule B), 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) 88.8 parts, 1.2 parts of styrene sulfonic acids, 1.0 parts of neopelexes, peroxide-2-ethyl hexanoic acid tert-butyl (day oily corporate system as polymerization initiator, trade name: Perbutyl O) 5 parts, reach 200 parts of ion exchange waters, 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 organic granular of average grain diameter 0.4 μ m.
From the seeding polymerization composition granule form beginning to the heat resisting temperature (T10 value) of the composition that obtains employed monomer (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and styrene sulfonic acid) till the non-conductive organic granular and non-conductive organic granular, adhesive can be as shown in table 1 with content and the metals content impurity of the crosslinked functional group's (sulfonic group) of heat cross-linking group (epoxy radicals).
(embodiment 7)
The non-conductive organic granular that obtains in operation (1)～(3) of replacement embodiment 1, use following non-conductive organic granular to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜non-conductive organic granular 〉
In possessing the reactor of mixer, put into 10 parts of the aqueous dispersions of the seeding polymerization composition granule B that operation (2) obtains (in the solid constituent benchmark, namely, weight basis in seeding polymerization composition granule B), 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) 89.4 parts, 0.6 part of methallylsulfonic acid, 1.0 parts of neopelexes, peroxide-2-ethyl hexanoic acid tert-butyl (day oily corporate system as polymerization initiator, trade name: Perbutyl O) 5 parts, reach 200 parts of ion exchange waters, 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 organic granular of average grain diameter 0.4 μ m.
From the seeding polymerization composition granule form beginning to the heat resisting temperature (T10 value) of the composition that obtains employed monomer (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and methallylsulfonic acid) till the non-conductive organic granular and non-conductive organic granular, adhesive can be as shown in table 1 with content and the metals content impurity of the crosslinked functional group's (sulfonic group) of heat cross-linking group (epoxy radicals).
(embodiment 8)
The non-conductive organic granular that obtains in operation (1)～(3) of replacement embodiment 1, use following non-conductive organic granular to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜non-conductive organic granular 〉
In possessing the reactor of mixer, put into 10 parts of the aqueous dispersions of the seeding polymerization composition granule B that operation (2) obtains (in the solid constituent benchmark, namely, weight basis in seeding polymerization composition granule B), 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) 88.7 parts, 1.3 parts of phosphoric acid-2-(methyl) acryloxy ethyl esters, 1.0 parts of neopelexes, peroxide-2-ethyl hexanoic acid tert-butyl (day oily corporate system as polymerization initiator, trade name: Perbutyl O) 5 parts, reach 200 parts of ion exchange waters, 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 organic granular of average grain diameter 0.4 μ m.
From the seeding polymerization composition granule form beginning to the heat resisting temperature (T10 value) of the composition that obtains employed monomer (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and phosphoric acid-2-(methyl) acryloxy ethyl ester) till the non-conductive organic granular and non-conductive organic granular, adhesive can be as shown in table 1 with content and the metals content impurity of the crosslinked functional group's (phosphate) of heat cross-linking group (epoxy radicals).
(embodiment 9)
The perforated membrane adhesive that obtains in the operation (4) of replacement embodiment 1, use following perforated membrane to make the perforated membrane slurry with adhesive, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜adhesive 〉
In possessing the reactor of mixer, put into 0.3 part of 70 parts of ion exchange waters, 0.4 part of neopelex and potassium peroxydisulfate, mix and obtain mixture, be warming up to 60 ℃.
On the other hand, 50 parts of hybrid ionic exchanged waters, 0.8 part of neopelex, 78 parts of 2-EHAs, 20.5 parts of acrylonitrile, 1.5 parts of allyl glycidyl ethers obtain monomer mixture in another container.
This monomer mixture was added in the said mixture continuously through 4 hours, make its polymerization.The temperature maintenance of reaction system is 60 ℃ in the interpolation process continuously, reacts.After adding end continuously, further continue reaction 3 hours down at 70 ℃, obtain containing the aqueous dispersions (adhesive aqueous dispersions) of adhesive.
After the adhesive aqueous dispersions that obtains is cooled to 25 ℃, to wherein adding ammoniacal liquor pH is adjusted to 7, imports steam then and remove unreacted monomer.Then, with respect to 100 parts of the solid constituents of adhesive, add 0.25 part of ethylenediamine tetra-acetic acid immediately, they are mixed, further carry out the adjustment of solid component concentration with ion exchange water on one side, stainless steel woven wire with 200 orders (the about 77 μ m of mesh) filters on one side, the perforated membrane aqueous dispersions of adhesive that obtains average grain diameter 100nm, solid component concentration 40%.
Perforated membrane with the polymerized unit of the vinyl monomer with heat cross-linking group (allyl glycidyl ether) in the adhesive contain that ratio is 1.5%, the polymerized unit of (methyl) acrylate monomer contain that ratio is 78%, α, the ratio that contains of the polymerized unit of alpha, beta-unsaturated nitriles monomer is 20.5%.
(embodiment 10)
The perforated membrane adhesive that obtains in the operation (4) of replacement embodiment 1, use following perforated membrane to make the perforated membrane slurry with adhesive, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜adhesive 〉
In possessing the reactor of mixer, put into 0.3 part of 70 parts of ion exchange waters, 0.4 part of neopelex and potassium peroxydisulfate, mix and obtain mixture, be warming up to 60 ℃.
On the other hand, 50 parts of hybrid ionic exchanged waters, 0.8 part of neopelex, 77.5 parts of 2-EHAs, 20 parts of acrylonitrile, 2.5 parts of 3-methacryloxy triethoxysilanes obtain monomer mixture in another container.
This monomer mixture was added in the said mixture continuously through 4 hours, make its polymerization.The temperature maintenance of reaction system is 60 ℃ in the interpolation process continuously, reacts.After adding end continuously, further continue reaction 3 hours down at 70 ℃, obtain containing the aqueous dispersions (adhesive aqueous dispersions) of adhesive.
After the adhesive aqueous dispersions that obtains is cooled to 25 ℃, to wherein adding ammoniacal liquor pH is adjusted to 7, imports steam then and remove unreacted monomer.Then, with respect to 100 parts of the solid constituents of adhesive, add 0.25 part of ethylenediamine tetra-acetic acid immediately, they are mixed, further carry out the adjustment of solid component concentration with ion exchange water on one side, stainless steel woven wire with 200 orders (the about 77 μ m of mesh) filters on one side, the perforated membrane aqueous dispersions of adhesive that obtains average grain diameter 100nm, solid component concentration 40%.
Perforated membrane with the polymerized unit of the vinyl monomer with heat cross-linking group in the adhesive (3-methacryloxy triethoxysilane) contain that ratio is 2.5%, the polymerized unit of (methyl) acrylate monomer contain that ratio is 77.5%, α, the ratio that contains of the polymerized unit of alpha, beta-unsaturated nitriles monomer is 20%.
(embodiment 11)
The non-conductive organic granular that obtains in operation (1)～(3) of replacement embodiment 1, use following non-conductive organic granular to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜non-conductive organic granular 〉
In possessing the reactor of mixer, put into 10 parts of the aqueous dispersions of the seeding polymerization composition granule B that operation (2) obtains (in the solid constituent benchmark, namely, weight basis in seeding polymerization composition granule B), 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) 85.5 parts, 4.5 parts of 2-acrylamides-2-methyl propane sulfonic acid, 1.0 parts of neopelexes, peroxide-2-ethyl hexanoic acid tert-butyl (day oily corporate system as polymerization initiator, trade name: Perbutyl O) 5 parts, reach 200 parts of ion exchange waters, 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 organic granular of average grain diameter 0.4 μ m.
From the seeding polymerization composition granule form beginning to the heat resisting temperature (T10 value) of the composition that obtains employed monomer (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and 2-acrylamide-2-methyl propane sulfonic acid) till the non-conductive organic granular and non-conductive organic granular, adhesive can be as shown in table 1 with content and the metals content impurity of the crosslinked functional group's (sulfonic group) of heat cross-linking group (epoxy radicals).
(embodiment 12)
The perforated membrane adhesive that obtains in the operation (4) of replacement embodiment 1, use following perforated membrane to make the perforated membrane slurry with adhesive, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜adhesive 〉
In possessing the reactor of mixer, put into 0.3 part of 70 parts of ion exchange waters, 0.4 part of neopelex and potassium peroxydisulfate, mix and obtain mixture, be warming up to 60 ℃.
On the other hand, 50 parts of hybrid ionic exchanged waters, 0.8 part of neopelex, 75 parts of 2-EHAs, 17 parts of acrylonitrile, 8 parts of glycidyl methacrylate obtain monomer mixture in another container.
This monomer mixture was added in the said mixture continuously through 4 hours, make its polymerization.The temperature maintenance of reaction system is 60 ℃ in the interpolation process continuously, reacts.After adding end continuously, further continue reaction 3 hours down at 70 ℃, obtain containing the aqueous dispersions (adhesive aqueous dispersions) of adhesive.
After the adhesive aqueous dispersions that obtains is cooled to 25 ℃, to wherein adding ammoniacal liquor pH is adjusted to 7, imports steam then and remove unreacted monomer.Then, with respect to 100 parts of the solid constituents of adhesive, add 0.25 part of ethylenediamine tetra-acetic acid immediately, they are mixed, further carry out the adjustment of solid component concentration with ion exchange water on one side, stainless steel woven wire with 200 orders (the about 77 μ m of mesh) filters on one side, the perforated membrane aqueous dispersions of adhesive that obtains average grain diameter 100nm, solid component concentration 40%.
Perforated membrane with the polymerized unit of the vinyl monomer with heat cross-linking group (glycidyl methacrylate) in the adhesive contain that ratio is 8%, the polymerized unit of (methyl) acrylate monomer contain that ratio is 75%, α, the ratio that contains of the polymerized unit of alpha, beta-unsaturated nitriles monomer is 17%.
(embodiment 13)
The perforated membrane adhesive that obtains in the operation (4) of replacement embodiment 1, use following perforated membrane to make the perforated membrane slurry with adhesive, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜adhesive 〉
In polymerization tank A, add 5 parts of styrene, 10 parts of butadiene, 3 parts of polyoxyethylene alkyl ethers (Emulgen1150S-60 processed of Kao Corp), reach 70 parts of ion exchange waters, fully stir.Then, temperature is made as 70 ℃, adds 0.3 part of water-soluble azo polymerization initiator as polymerization initiator (with the pure pharmaceutical worker of light VA-086 processed already), and 10 parts of ion exchange waters, stirred 120 minutes.
On the other hand, in another polymerization tank B, add 45.8 parts of styrene, 36.9 parts of butadiene, 2.3 parts of glycidyl methacrylate, 10 parts of polyoxyethylene alkyl ethers and 30 parts of ion exchange waters and stir, made emulsion.
Then, after being added continuously to polymerization tank A from polymerization tank B in about 300 minutes, stir about 180 minutes reaches at 95% o'clock in monomer consumption and cools off, and finishes reaction with the emulsion of making.Thus, obtain solid component concentration is 40%, number average particle diameter is 150nm perforated membrane with the aqueous dispersions of adhesive.
Perforated membrane contains with the polymerized unit of the vinyl monomer with heat cross-linking group (glycidyl methacrylate) in the adhesive that ratio is 2.3%, polymerized unit and the α of (methyl) acrylate monomer, and the ratio that contains of the polymerized unit of alpha, beta-unsaturated nitriles monomer is 0%.
(embodiment 14)
Be coated with the perforated membrane slurry that obtains in the operation (5) of embodiment 1 in the mode that to cover negative electrode active material layer and dried perforated membrane thickness fully be 5 μ m on the face of negative electrode active material layer one side of the negative pole that in the operation (7) of embodiment 1, obtains, obtain pulp layer.Pulp layer was descended dry 10 minutes at 50 ℃, form perforated membrane, obtain the negative pole with perforated membrane.The negative pole of the band perforated membrane that obtains has the such layer of (perforated membrane)/(negative electrode active material layer)/(Copper Foil) and constitutes.Flexibility, the mealiness that falls and amount of moisture to the negative pole of the band perforated membrane that obtains are estimated.The result is as shown in table 1.
The organic dividing plate that replaces the band perforated membrane that obtains in the operation (8) of embodiment 1, used organic dividing plate (polypropylene of individual layer dividing plate processed, the porosity 55%, thickness 25 μ m, with the operation (8) 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 (7) of embodiment 1, used the negative pole of above-mentioned band perforated membrane, in addition, carry out operation similarly to Example 1, obtained secondary cell and estimate.The result is as shown in table 1.Need to prove, when being positioned in the negative pole of the band perforated membrane of circle in the outer packaging container, with the face of its perforated membrane one side mode mounting towards the face of organic dividing plate one side of circle, Copper Foil one side towards upside.
(embodiment 15)
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＜adhesive 〉
The perforated membrane that obtains in the operation (4) of embodiment 1 is with 100 parts of (solid constituent is 40%) 760 parts of NMP of middle interpolation of aqueous dispersion of adhesive and after abundant the mixing, under 90 ℃ of reduced pressure atmosphere, remove water and NMP in the system, obtain perforated membrane with the NMP dispersion (solid constituent is 10%) of adhesive.
The manufacturing of＜perforated membrane slurry 〉
NMP dispersion and the perforated membrane of the non-conductive particle that obtains in the above-mentioned operation are mixed than the mode that is 87:13 with solid constituent with the NMP dispersion of adhesive, obtain the perforated membrane slurry of solid component concentration 18%.
The manufacturing of the negative pole of＜band perforated membrane 〉
Be coated with the perforated membrane slurry that obtains in the above-mentioned operation in the mode that to cover negative electrode active material layer and dried perforated membrane thickness fully be 5 μ m on the face of negative electrode active material layer one side of the negative pole that in the operation (7) of embodiment 1, obtains, obtain pulp layer.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 of (perforated membrane)/(negative electrode active material layer)/(Copper Foil) and constitutes.Flexibility, the mealiness that falls and amount of moisture to the negative pole of the band perforated membrane that obtains are estimated.The result is as shown 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 (8) of embodiment 1, used organic dividing plate (polypropylene of individual layer dividing plate processed, the porosity 55%, thickness 25 μ m, with the operation (8) 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 (7) of embodiment 1, used the negative pole of above-mentioned band perforated membrane, in addition, carry out operation similarly to Example 1, obtained secondary cell and estimate.The result is as shown in table 1.Need to prove, when being positioned in the negative pole of the band perforated membrane of circle in the outer packaging container, with the face of its perforated membrane one side mode mounting towards the face of organic dividing plate one side of circle, Copper Foil one side towards upside.
(comparative example 1)
The perforated membrane adhesive that obtains in the operation (4) of replacement embodiment 1, use following perforated membrane to make the perforated membrane slurry with adhesive, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜adhesive 〉
In possessing the reactor of mixer, put into 0.3 part of 70 parts of ion exchange waters, 0.4 part of neopelex and potassium peroxydisulfate, mix and mixture, be warming up to 60 ℃.
On the other hand, 50 parts of hybrid ionic exchanged waters, 0.8 part of neopelex, 79 parts of 2-EHAs, 21 parts of acrylonitrile obtain monomer mixture in another container.
This monomer mixture was added in the said mixture continuously through 4 hours, make its polymerization.The temperature maintenance of reaction system is 60 ℃ in the interpolation process continuously, reacts.After adding end continuously, further continue reaction 3 hours down at 70 ℃, obtain containing the aqueous dispersions (adhesive aqueous dispersions) of adhesive.
After the adhesive aqueous dispersions that obtains is cooled to 25 ℃, to wherein adding ammoniacal liquor pH is adjusted to 7, imports steam then and remove unreacted monomer.Then, with respect to 100 parts of the solid constituents of adhesive, add 0.25 part of ethylenediamine tetra-acetic acid immediately, they are mixed, further carry out the adjustment of solid component concentration with ion exchange water on one side, stainless steel woven wire with 200 orders (the about 77 μ m of mesh) filters on one side, the perforated membrane aqueous dispersions of adhesive that obtains average grain diameter 100nm, solid component concentration 40%.
Perforated membrane with the polymerized unit of the vinyl monomer with heat cross-linking group in the adhesive contain that ratio is 0%, the polymerized unit of (methyl) acrylate monomer contain that ratio is 79%, α, the ratio that contains of the polymerized unit of alpha, beta-unsaturated nitriles monomer is 21%.
(comparative example 2)
The non-conductive organic granular that obtains in operation (1)～(3) of replacement embodiment 1, use following non-conductive organic granular to make the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜non-conductive organic granular 〉
In possessing the reactor of mixer, put into 10 parts of the aqueous dispersions of the seeding polymerization composition granule B that operation (2) obtains (in the solid constituent benchmark, namely, weight basis in seeding polymerization composition granule B), 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, 1.0 parts of neopelexes, peroxide-2-ethyl hexanoic acid tert-butyl (day oily corporate system as polymerization initiator, trade name: Perbutyl O) 5 parts, reach 200 parts of ion exchange waters, 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 organic granular of average grain diameter 0.4 μ m.
It is as shown in table 1 to heat resisting temperature (T10 value) and the metals content impurity of the composition that obtains employed monomer (styrene, methacrylic acid, divinylbenzene and vinyl xylene, ethyl vinyl benzene) till the non-conductive organic granular and non-conductive organic granular to form beginning from the seeding polymerization composition granule.
(comparative example 3)
The perforated membrane adhesive that obtains in the operation (4) of replacement embodiment 1, use following perforated membrane to make the perforated membrane slurry with adhesive, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
The manufacturing of＜adhesive 〉
In polymerization tank A, add 5 parts of styrene, 10 parts of butadiene, 3 parts of polyoxyethylene alkyl ethers (Emulgen1150S-60 processed of Kao Corp), reach 70 parts of ion exchange waters, fully stir.Then, temperature is made as 70 ℃, adds 0.3 part of water-soluble azo polymerization initiator as polymerization initiator (with the pure pharmaceutical worker of light VA-086 processed already), and 10 parts of ion exchange waters, stirred 120 minutes.
On the other hand, in another polymerization tank B, add 47 parts of styrene, 38 parts of butadiene, 10 parts of polyoxyethylene alkyl ethers, and 30 parts of ion exchange waters and stirring, made emulsion.
Then, after being added continuously to polymerization tank A from polymerization tank B in about 300 minutes, stir about 180 minutes reaches at 95% o'clock in monomer consumption and cools off, and finishes reaction with the emulsion of making.Obtain solid component concentration thus and be 40%, number average particle diameter is the perforated membrane of 150nm with the aqueous dispersions of adhesive.
Perforated membrane contains ratio, and α with the polymerized unit that contains ratio, (methyl) acrylate monomer of the polymerized unit of the vinyl monomer with heat cross-linking group in the adhesive, and the ratio that contains of the polymerized unit of alpha, beta-unsaturated nitriles monomer is 0%.
(comparative example 4)
The non-conductive organic granular that obtains in operation (1)～(3) of replacement embodiment 1, the Alumana AKP-50 (average grain diameter 0.3 μ m) that uses sumitomo chemical company to make has made the perforated membrane slurry, in addition, carry out operation similarly to Example 1, obtained being with organic dividing plate and the secondary cell of perforated membrane and estimating.The result is as shown in table 1.
[table 1]
Figure BDA00003276409000491
The following content of deducibility as a result by table 1.
Have the secondary battery separator that uses the secondary cell perforated membrane that following secondary cell perforated membrane slurry (embodiment 1～15) forms and the flexibility of electrode for secondary battery, the mealiness that falls excellence, described secondary cell perforated membrane slurry (embodiment 1～15) comprises: comprise the vinyl monomer with heat cross-linking group polymerized unit adhesive and have can with the non-conductive organic granular of the crosslinked functional group of this heat cross-linking group.And amount of moisture contained in the above-mentioned perforated membrane is few, and tenor is few.Its result can suppress the side reaction in the secondary cell, makes battery behavior raisings such as cycle characteristics.Wherein, has the secondary battery separator that uses the secondary cell perforated membrane that following secondary cell perforated membrane forms with slurry (embodiment 1～7 and 14,15) and the flexibility of electrode for secondary battery, the mealiness that falls excellence especially, moisture in the perforated membrane and tenor are also few, demonstrate excellent cycle characteristics, described secondary cell perforated membrane comprises with slurry (embodiment 1～7 and 14,15): comprise have sulfonic group as the non-conductive organic granular of hydrophily acidic-group and have the epoxy radicals conduct can with the adhesive of the crosslinked functional group of hydrophily acidic-group.
On the other hand, use the adhesive do not have the heat cross-linking group situation (comparative example 1,3), use and do not have and can and use inorganic particle (aluminium oxide) to replace under the situation (comparative example 4) of non-conductive organic granular with the situation (comparative example 2) of the non-conductive organic granular of the crosslinked functional group of heat cross-linking group, the flexibility of secondary battery separator and electrode for secondary battery, the mealiness that falls are poor, so the cycle characteristics deterioration.Wherein, use inorganic particle (aluminium oxide) to replace under the situation (comparative example 4) of non-conductive organic granular, amount of moisture contained in the perforated membrane is many, and the content of metal impurities is many, and therefore, cycle characteristics is poor especially.

Claims (11)

1. secondary cell perforated membrane slurry, it comprises:
Comprise the adhesive that the polymerized unit of the vinyl monomer with heat cross-linking group forms,
Have can with the non-conductive organic granular of the crosslinked functional group of this heat cross-linking group, and solvent.
2. secondary cell perforated membrane slurry according to claim 1, wherein,
Described adhesive also contains polymerized unit and the α of (methyl) acrylate monomer, the polymerized unit of alpha, beta-unsaturated nitriles monomer,
In whole polymerized units, the ratio that contains of the polymerized unit of described vinyl monomer with heat cross-linking group is 0.1～10 quality %, the ratio that contains of the polymerized unit of described (methyl) acrylate monomer is 50～98 quality %, described α, the polymerized unit of alpha, beta-unsaturated nitriles monomer are 1.0～50 quality %.
3. secondary cell perforated membrane slurry according to claim 1 and 2, wherein,
Described heat cross-linking group is epoxy radicals or pi-allyl.
4. according to each described secondary cell perforated membrane slurry in the claim 1～3, wherein,
The average grain diameter of described non-conductive organic granular is 0.1～2.0 μ m, and
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 organic granular reaches 10 quality % is more than 250 ℃ with thermobalance.
5. according to each described secondary cell perforated membrane slurry in the claim 1～4, wherein,
With respect to non-conductive organic granular, described can be 0.008～0.240mmol/g with the content of the crosslinked functional group of heat cross-linking group.
6. according to each described secondary cell perforated membrane slurry in the claim 1～5, wherein,
Described can be sulfonic group or phosphate with the crosslinked functional group of heat cross-linking group.
7. secondary cell perforated membrane, it is by forming membranaceous and dry obtaining with each described secondary cell perforated membrane slurry in the claim 1～6.
8. secondary cell perforated membrane, it comprises:
Comprise the adhesive that the polymerized unit of the vinyl monomer with heat cross-linking group forms, and
Have can with the non-conductive organic granular of the crosslinked functional group of this heat cross-linking group,
Wherein, between described adhesive and described non-conductive organic granular, has cross-linked structure.
9. electrode for secondary battery, it comprises:
Collector body,
Electrode active material layer, it is attached to this collector body and comprises electrode active material and binding agent for electrode, and
Be stacked in the lip-deep claim 7 of this electrode active material layer or 8 described secondary cell perforated membranes.
10. secondary battery separator, it comprises:
Organic dividing plate, and
Be stacked in claim 7 or 8 described secondary cell perforated membranes on this organic dividing plate.
11. a secondary cell, it comprises:
Positive pole, negative pole, organic dividing plate and electrolyte,
Wherein, have the right requirement 7 or 8 described secondary cell perforated membranes of any superimposed layer in described positive pole, negative pole and organic dividing plate.
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