CN103238234B - Secondary cell perforated membrane slurry, secondary cell perforated membrane, electrode for secondary battery, secondary battery separator and secondary cell - Google Patents

Secondary cell perforated membrane slurry, secondary cell perforated membrane, electrode for secondary battery, secondary battery separator and secondary cell Download PDF

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Publication number
CN103238234B
CN103238234B CN201180057788.4A CN201180057788A CN103238234B CN 103238234 B CN103238234 B CN 103238234B CN 201180057788 A CN201180057788 A CN 201180057788A CN 103238234 B CN103238234 B CN 103238234B
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perforated membrane
binding agent
secondary cell
monomer
organic granular
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CN103238234A (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 & Material Sciences (AREA)
  • 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

It is an object of the invention to provide the secondary cell perforated membrane that the secondary cell perforated membrane slurry of a kind of excellent dispersion using screening characteristics and non-conductive organic granular manufactures, this secondary cell perforated membrane can make the cycle characteristics of gained secondary cell improve, its flexibility is high, it is possible to prevent powder falling, and the water quantities contained is few.It addition, the present invention also aims to provide the content of a kind of metal impurities few, it is adaptable to the non-conductive organic granular of secondary cell perforated membrane.For this, the present invention provides a kind of secondary cell perforated membrane slurry, and it contains: the binding agent of the polymerized unit comprising the vinyl monomer with heat cross-linking group, the non-conductive organic granular with the functional group that can cross-link with this heat cross-linking group and 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 manufacturing It is formed at the electrode of lithium rechargeable battery or baffle surface, flexibility high and can help to the circulation of battery The secondary cell perforated membrane slurry of the secondary cell perforated membrane of the improvement of characteristic.Moreover, it relates to one Plant electrode for secondary battery, secondary battery separator and the secondary cell possessing this secondary cell perforated membrane.
Background technology
In the most practical battery, lithium rechargeable battery demonstrates the highest energy density, particularly It is used for miniaturized electronics purposes.It addition, in addition to small utility, be also contemplated that and launch to automotive field. Wherein, it is desirable to the long lifetime of lithium rechargeable battery and the further raising of safety.
In order to prevent the short circuit between positive pole and negative pole, lithium rechargeable battery generally uses polyethylene, The organic dividing plate of the TPO such as polypropylene.Owing to the organic dividing plate of TPO has below 200 DEG C melted Physical property, therefore, in the case of battery reaches a high temperature because of stimulation internally and/or externally, it may occur that have The contraction of machine dividing plate, melted etc., cause the volume of organic dividing plate to change.It is as a result, it is possible to draw Play positive pole and the short circuit of negative pole, set off an explosion because of the release of electric energy etc..
In order to solve such problem resulting from and using the organic dividing plate of TPO, it has been proposed that following side Case: on the organic dividing plate of TPO or electrode (positive pole, negative pole) superimposed layer to contain inorganic particle etc. non-conductive The layer (perforated membrane) of property granule.Additionally, for the thermal runaway preventing the abnormal response of battery from causing, it has been suggested that A kind of perforated membrane, described perforated membrane contain melt because being heated polymer beads, at electrolyte In the polymer beads that rises because being heated of swellbility.It is considered to have following function: at secondary electricity The temperature in pond due to short circuit etc. abnormal rise in the case of, this polymer beads is because of melted or swelling and stifled Plug perforated membrane in fine hole, thus stop interelectrode ion to pass through, therefore have blocking-up electric current, The further up function (cutting function) of suppression temperature.
In patent documentation 1, such as record a kind of perforated membrane, in order to improve safety, made this perforated membrane Containing heat-resistant resin microgranule and the organic fine particles with cutting function.It addition, wherein also stated that use Ethane-acetic acid ethyenyl ester polymer is as perforated membrane binding agent.
Patent documentation 2 is recorded and has gathered by sulfonic acid etc. being had the water-dispersible acrylic of hydrophilic radical Polymer beads is used as the method that binding agent prevents the non-conductive granule powder falling from perforated membrane.It addition, also Describe the description below: by making water-dispersible acrylic's polymer beads has further bridging property base Group, can have tough and tensile and soft perforated membrane.
Patent documentation 3 has been recorded a kind of use aluminium oxide, titanium oxide as inorganic filler, use poly-second Enol, SB are as the perforated membrane of binding agent.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-139978 publication
Patent documentation 2: International Patent Publication WO2009/123168
Patent documentation 3: Japanese Unexamined Patent Publication 2008-210794 publication
Summary of the invention
The problem that invention is to be solved
But, according to the research of the present inventor, the perforated membrane described in patent documentation 1 due to use ethylene- Vinyl acetate polymer is as binding agent, therefore, and the thermostability in the slurry forming this perforated membrane The dispersibility of resin particle and organic fine particles is insufficient, the lack of homogeneity of perforated membrane.Its result is the most The flexibility of pore membrane is deteriorated.If it addition, use ethane-acetic acid ethyenyl ester polymer as binding agent, then having Shi Wufa keeps the caking property of heat-resistant resin microgranule and organic fine particles fully, may cause this microgranule certainly Perforated membrane departs from (powder falling).
For the perforated membrane described in patent documentation 2, it is known that although non-conductive granule is starched at perforated membrane Excellent dispersion in material, but containing hydrophilic radical in as the acroleic acid polymerization composition granule of binding agent In the case of crosslinkable groups, owing to there is the functional group mutually with reactivity, thus there is slurry Manufacturing process crosslinks the tendency of reaction.Therefore, the screening characteristics of slurry in time through and become Instability, its result, the flexibility of perforated membrane may be caused to become insufficient.
For the perforated membrane described in patent documentation 3, may be because moisture contained in perforated membrane be at electricity Side reaction is occurred to cause cycle characteristics to reduce in pond, furthermore, it is possible to can be because of gold contained in inorganic filler Belonging to impurity occurs Ion release to cause cycle characteristics to reduce in the battery.
Therefore, it is an object of the invention to provide a kind of use screening characteristics and non-conductive organic granular point Dissipate the secondary cell perforated membrane that the excellent secondary cell perforated membrane slurry of property manufactures, this secondary cell perforated membrane The cycle characteristics that can make gained secondary cell improves, and its flexibility is high, is possible to prevent powder falling, and contain Water quantities is few.
To this end, present inventor has performed research, it was found that by using specific binding agent and specific Non-conductive organic granular, the perforated membrane that flexibility and powder falling are excellent can be obtained.It is to say, By using specific binding agent and specific non-conductive organic granular, slurry manufacturing process can be suppressed In cross-linking reaction, reduce slurry thickening etc..Therefore, it can improve non-conductive organic granular many Dispersibility in pore membrane slurry and the screening characteristics of perforated membrane slurry, it is possible to obtain the much higher pore membrane of flexibility. Further, since forming cross-linked structure between the binding agent and non-conductive organic granular of the present invention, Therefore, the caking property of binding agent and non-conductive organic granular becomes good, is possible to prevent non-conductive to have Machine granule departs from (powder falling) from perforated membrane.Further, since the non-conductive organic granular in the present invention does not comes From the Ion release of inorganic filler, the water content of perforated membrane is few, therefore, battery behavior also will not be made to be deteriorated. Additionally, the present inventors have additionally discovered that, by improving the dispersion of the non-conductive organic granular in perforated membrane slurry Property and the screening characteristics of perforated membrane slurry, be possible not only to improve perforated membrane productivity, additionally it is possible to improve use The cycle characteristics of the secondary cell of this perforated membrane.
The method of solution problem
In order to solve above-mentioned problem, the purport of the present invention is as described below.
(1) a kind of secondary cell perforated membrane slurry, it contains: comprise the vinyl with heat cross-linking group The binding agent of the polymerized unit of monomer, have and can lead with the non-of functional group of this heat cross-linking group crosslinking Electrically organic granular and solvent.
(2) according to the secondary cell perforated membrane slurry described in (1), wherein, described binding agent is possibly together with (methyl) The polymerized unit of acrylate monomer and α, the polymerized unit of alpha, beta-unsaturated nitriles monomer,
In whole polymerized units, described in there is the polymerized unit of vinyl monomer of heat cross-linking group Be 0.1～10 mass % containing ratio, the polymerized unit of described (methyl) acrylate monomer containing ratio be 50～98 mass %, described α, the polymerized unit of alpha, beta-unsaturated nitriles monomer is 1.0～50 mass %.
(3) according to the secondary cell perforated membrane slurry described in (1) or (2), wherein, described heat cross-linking group For epoxy radicals or pi-allyl.
(4) according to the secondary cell perforated membrane slurry according to any one of (1)～(3), wherein, described non-conductive The mean diameter of property organic granular is 0.1～2.0 μm,
Further, when heating with programming rate 10 DEG C/min under nitrogen atmosphere with thermobalance, described non-conductive It is more than 250 DEG C that the loss of weight ratio of organic granular reaches the temperature of 10 mass %.
(5) according to the secondary cell perforated membrane slurry according to any one of (1)～(4), wherein, lead relative to non- Electrically organic granular, described can be with the content of the functional group of heat cross-linking group crosslinking 0.008～0.240mmol/g.
(6) according to secondary cell perforated membrane slurry according to any one of (1)～(5), wherein, described can be with The functional group of heat cross-linking group crosslinking is sulfonic group or phosphate.
(7) a kind of secondary cell perforated membrane, it is by by the secondary cell according to any one of above-mentioned (1)～(6) Perforated membrane slurry is formed as membranaceous and dry and obtains.
(8) a kind of secondary cell perforated membrane, it comprises: comprise the vinyl monomer with heat cross-linking group The binding agent of polymerized unit and have can non-conductive with the functional group of this heat cross-linking group crosslinking Property organic granular,
Between described binding agent and described non-conductive organic granular, there is cross-linked structure.
(9) a kind of electrode for secondary battery, it contains: collector body, is attached to this collector body and comprises electrode active Property material and the electrode active material layer of binding agent for electrode and be stacked in this electrode active material layer table The secondary cell perforated membrane described in (7) or (8) on face.
(10) a kind of secondary battery separator, its contain organic dividing plate, (7) that are stacked on this organic dividing plate or (8) the secondary cell perforated membrane described in.
(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 two described in (7) or (8) Primary cell perforated membrane.
The effect of invention
According to the present invention it is possible to provide a kind of secondary cell perforated membrane slurry, described secondary cell perforated membrane Slurry is used for manufacturing secondary cell perforated membrane, and described secondary cell perforated membrane is by gluing containing specific composition Mixture and specific non-conductive organic granular, flexibility and powder falling are excellent, can help to secondary cell The raising of cycle characteristics.It addition, the dispersibility of this perforated membrane slurry and screening characteristics are excellent.Additionally, by Few in the water content of the secondary cell perforated membrane using this perforated membrane slurry to manufacture, therefore, also will not occur The deterioration of battery behavior.It addition, by this perforated membrane is stacked on electrode surface, be possible to prevent electrode active The disengaging of property material.It is furthermore possible to also provide a kind of, digestion of metallic ion will not occur in the secondary battery Non-conductive organic granular.
Detailed description of the invention
Hereinafter, to (1) secondary cell perforated membrane slurry of the present invention, (2) secondary cell perforated membrane, (3) secondary Battery electrode, (4) secondary battery separator and (5) secondary cell illustrate successively.
(1) secondary cell perforated membrane slurry
The secondary cell perforated membrane slurry (being the most also denoted as " perforated membrane slurry ") of the present invention is for after being formed The slurry of the secondary cell perforated membrane stated.Perforated membrane slurry contains the binding agent of specific composition and the most non- Electric conductivity organic granular, is using as this binding agent of solid constituent, this non-conductive organic granular and appoint The composition of meaning is dispersed to be obtained in a solvent.
(binding agent)
Binding agent for the present invention comprises the polymerized unit of the vinyl monomer with heat cross-linking group. In the present invention, the polymerized unit comprising the vinyl monomer with heat cross-linking group by use forms Binding agent, good caking property can be given to binding agent, can improve non-conductive with described later simultaneously The reactivity of organic granular.Its result, available caking property is high and powder falling much less pore membrane, it addition, can So that using the cycle characteristics of the secondary cell of this perforated membrane to improve.
As the heat cross-linking group of the vinyl monomer with heat cross-linking group for the present invention, can Enumerate epoxy radicals, N-methylol amide base,Oxazoline base, pi-allyl, NCO, oxa-ring fourth Base, alkoxysilane group etc..Wherein, owing to the regulation of crosslinking and crosslink density is easy, therefore preferred ring Epoxide or pi-allyl, particularly preferred epoxy radicals.It should be noted that the kind of cross-linking functional group is permissible It it is a kind, it is also possible to for two or more.
As having the vinyl monomer of epoxy radicals, such as, can enumerate containing carbon-to-carbon double bond and epoxy radicals Monomer.
As the monomer containing carbon-to-carbon double bond and epoxy radicals, such as, can enumerate: vinyl glycidyl ether, The unsaturations such as allyl glycidyl ether, cyclobutenyl glycidyl ether, o-allyl base glycidyl ether Glycidyl ether；Butadiene monoepoxide, chlorobutadiene monoepoxide, 4,5-epoxy-2-amylene, 3,4- Diene or the mono-epoxide of polyenoid such as epoxy-1-VCH, 1,2-epoxy-5,9-ring 12 carbon diene Thing；The alkenyl epoxides such as 3,4-epoxy-1-butylene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene； Glycidyl acrylate, glycidyl methacrylate .beta.-methylacrylic acid ethylene oxidic ester, (+)-2,3-Epoxy-1-propanol Base-4-heptenoic acid esters, sorbic acid ethylene oxidic ester, linoleic acid ethylene oxidic ester, glycidyl-4-methyl -3-pentenoate, the glycidyl esters of 3-cyclohexene carboxylate, 4-methyl-3-cyclohexene carboxylate shrink sweet The glycidyl esters etc. of the unsaturated carboxylic acids such as oil base ester.
As having the vinyl monomer of N-methylol amide base, such as, can enumerate: N-methylol (methyl) Acrylamides etc. have (methyl) acrylic amide etc. of methylol.
As havingThe vinyl monomer of oxazoline base, such as, can enumerate: 2-vinyl-2-Oxazoline, 2-vinyl-4-methyl-2-Oxazoline, 2-vinyl-5-methyl-2-Oxazoline, 2-isopropenyl-2-Oxazoline, 2-isopropenyl-4-methyl-2-Oxazoline, 2-isopropenyl-5-methyl-2-Oxazoline, 2-isopropenyl-5-second Base-2-Oxazoline etc..
As having the vinyl monomer of pi-allyl, such as, can enumerate: allyl acrylate, methyl Allyl acrylate, allyl glycidyl ether etc..
As having the vinyl monomer of NCO, such as, can enumerate: vinyl isocyanate, Allyl iso cyanurate, (methyl) acrylic acid isocyanates, 2-(methyl) acryloyloxyethyl isocyanate, 2-isocyanate ethyl (methyl) acrylate, an isopropenyl-alpha, alpha-dimethyl methylbenzyl isocyanate Deng.
As having the vinyl monomer of oxetanylmethoxy, such as, can enumerate: 3-((methyl) acryloyl-oxy Ylmethyl) oxetanes, 3-((methyl) acryloyloxymethyl)-2-trifluoromethyl oxetanes, 3-((first Base) acryloyloxymethyl)-2-phenyl oxetanes, 2-((methyl) acryloyloxymethyl) oxa-ring fourth Alkane, 2-((methyl) acryloyloxymethyl)-4-trifluoromethyl oxetanes etc..
As having the vinyl monomer of alkoxysilane group, can enumerate: vinyltrimethoxy silane, VTES, methacryloyloxypropyl methyl dimethoxysilane, methacryl Epoxide propyl trimethoxy silicane, methacryloyloxypropyl methyl diethoxy silane, metering system Acryloxypropylethoxysilane triethoxysilane, 3-methacryloxy triethoxysilane etc..
In whole polymerized units of binding agent, there is the polymerization list of the vinyl monomer of heat cross-linking group Unit is preferably 0.1～10 mass %, more preferably 0.3～7 mass %, particularly preferably 0.5～5 containing ratio Quality %.If whole polymerized units of binding agent have the polymerization of the vinyl monomer of heat cross-linking group Unit containing ratio within the above range, then with the reactive raising of non-conductive organic granular described later, In perforated membrane slurry, the dispersion stabilization of non-conductive organic granular is excellent.Further, the caking property of binding agent Improve, non-conductive organic granular can be suppressed to depart from (powder falling) from perforated membrane.
In the present invention, it is preferred to binding agent contains the polymerized unit of (methyl) acrylate monomer further.Logical Crossing the polymerized unit making binding agent contain (methyl) acrylate monomer, binding agent will not be at the electricity of secondary cell Solve liquid dissolution, can be shown that appropriate swellability in the electrolytic solution, therefore, it can keep well lithium The conductivity of ion.It is as a result, it is possible to increase the cycle characteristics of secondary cell.
In whole polymerized units of binding agent, the polymerized unit of (methyl) acrylate monomer containing ratio It is preferably 50～98 mass %, more preferably 60～97.5 mass %, particularly preferably 65～95 mass %. By make the polymerized unit of (methyl) acrylate monomer in whole polymerized units of binding agent containing ratio Within the above range, can moderately keep the mobility of polymer, improve non-conductive organic granular Dispersion stabilization and the flexibility of perforated membrane.Furthermore it is possible to improve the cycle characteristics of secondary cell.
As (methyl) acrylate monomer, can enumerate: acrylic acid methyl ester., ethyl acrylate, acrylic acid N-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, amyl acrylate, propylene Acid own ester, heptylacrylate, 1-Octyl acrylate, 2-EHA, acrylic acid nonyl ester, propylene The acrylic acid alkyls such as acid ester in the last of the ten Heavenly stems, lauryl acrylate, n-myristyl base ester, stearyl acrylate ester Ester；Methyl methacrylate, ethyl methacrylate, n propyl methacrylate, methacrylic acid are different Propyl ester, n-BMA, Tert-butyl Methacrylate, pentylmethacrylate, metering system Acid own ester, metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, 2-Ethylhexyl Methacrylate, methyl Acrylic acid nonyl ester, decyl-octyl methacrylate, lauryl methacrylate, methacrylic acid n-tetradecane base The alkyl methacrylate such as ester, stearyl methacrylate.Wherein, due to electrolyte will not dissolution, Can be swelling and demonstrate the conductivity of lithium ion by appropriateness in the electrolytic solution, and, non-conductive The dispersion of organic granular is not susceptible to the cross-linked cohesion caused by polymer, the most preferably with non-carbonyl The atomic number of alkyl carbon of oxygen atoms bond is (methyl) ethyl acrylate, the positive fourth of (methyl) acrylic acid of 2～13 Ester, (methyl) 2-EHA, (methyl) lauryl acrylate, the most more preferably with non-carbonyl The atomic number of alkyl carbon of oxygen atoms bond is (methyl) n-butyl acrylate, (methyl) acrylic acid 2-of 4～10 Octyl Nitrite.
It addition, in the present invention, it is preferred to binding agent contains α further, the polymerization list of alpha, beta-unsaturated nitriles monomer Unit.By making binding agent contain α, the polymerized unit of alpha, beta-unsaturated nitriles monomer, the intensity of binding agent can be improved.
In whole polymerized units of binding agent, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer excellent containing ratio Elect 1.0～50 mass %, more preferably 2.5～40 mass %, particularly preferably 5～35 mass % as.Pass through Make the polymerized unit of 'alpha ', ' bela '-unsaturated nitrile monomer in whole polymerized units of binding agent containing ratio above-mentioned In the range of, can moderately keep the mobility of polymer in perforated membrane slurry, improve non-conductive organic The dispersion stabilization of granule and the flexibility of perforated membrane.Furthermore it is possible to improve the cycle characteristics of secondary cell.
As α, alpha, beta-unsaturated nitriles monomer, can enumerate: acrylonitrile or methacrylonitrile.
Additionally, for for the binding agent of the present invention, except above-mentioned polymerized unit (that is, has heat friendship The connection property polymerized unit of vinyl monomer of group, the polymerized unit of (methyl) acrylate monomer and α, β- The polymerized unit of unsaturated nitrile monomer) beyond, preferably single possibly together with being polymerized with other of their copolymerization Unit.In whole polymerized units of binding agent other polymerized unit be preferably 0.1～10 mass % containing ratio, More preferably 0.1～5 mass %.If other polymerized unit containing ratio in whole polymerized units of binding agent Within the above range, then non-conductive organic granular dispersibility in perforated membrane slurry will not be occurred to reduce, Perforated membrane can be formed uniformly.
As other polymerized unit, can enumerate: styrene, chlorostyrene, vinyltoluene, tertiary fourth Base styrene, vinyl benzoic acid, vinylbenzoate, vinyl naphthalene, 1-chloro-4-methyl-benzene, α- The styrene monomer such as methyl styrene, divinylbenzene；
Acrylic acid, methacrylic acid .beta.-methylacrylic acid, 2-ethylacrylic acid, iso-crotonic acid, α-acetoxyl group third Olefin(e) 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 the ethylene of dicarboxylic acids Class unsaturated carboxylic acid and derivant thereof；
The olefines such as ethylene, propylene；The diene-based monomer such as butadiene, isoprene；
The halogen atom monomer such as vinyl chloride, vinylidene chloride；
The vinyl esters such as vinyl acetate, propionate, vinyl butyrate；
The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether；
Methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, isopropyl alkene The vinyl ketones such as base vinyl ketone；
The vinyl compound containing heterocycle such as NVP, vinylpyridine, vinyl imidazole；
The amide-type monomer such as acrylamide, Methacrylamide etc..
It should be noted that binding agent can contain only a kind of other polymerized unit, it is also possible to arbitrarily Ratio combine contains two or more other polymerized unit.
For the binding agent of the present invention at the dispersion liquid being scattered in disperse medium (water or organic solvent) and formed State under use, or make when the solution being dissolved in disperse medium (water or organic solvent) and formed With (following, also they are referred to as " binding agent dispersion liquid ".).In the present invention, excellent in terms of environment From the viewpoint of different, rate of drying is fast, water is preferably used as disperse medium.It addition, it is organic using In the case of solvent is as disperse medium, the organic solvents such as N-Methyl pyrrolidone (NMP) can be used.
In the case of binding agent is scattered in disperse medium with graininess, with the scattered binding agent of graininess Mean diameter (dispersion particle diameter) is preferably 50～500nm, more preferably 70～400nm, most preferably 100～250nm.If the mean diameter of binding agent is above-mentioned scope, then the intensity of the second electrode obtained and Flexibility becomes good.
In the case of binding agent is scattered in disperse medium with graininess, the solid component concentration of dispersion liquid leads to It is often 15～70 mass %, preferably 20～65 mass %, more preferably 30～60 mass %.Gu if Body constituent concentration is above-mentioned scope, then operability when manufacturing perforated membrane slurry is good.
Glass transition temperature (Tg) for the binding agent of the present invention is preferably-50～25 DEG C, more preferably -45～15 DEG C, particularly preferably-40～5 DEG C.By make the Tg of binding agent in above-mentioned scope, the present invention's Perforated membrane has intensity and the flexibility of excellence, therefore can improve secondary cell defeated using this perforated membrane Go out characteristic.It should be noted that the glass transition temperature of binding agent can be by by various combination of monomers It is adjusted.
Manufacture method as the polymer of the binding agent for the present invention is not particularly limited, it is possible to use Any means in solution polymerization process, suspension polymerization, mass polymerization, emulsion polymerization etc..As Polyreaction, it would however also be possible to employ any in ionic polymerization, radical polymerization, active free radical polymerization etc. Reaction.As the polymerization initiator for polymerization, such as lauroyl peroxide, diisopropyl can be enumerated Peroxy dicarbonate, two-2-ethylhexyl peroxy dicarbonates, t-butylperoxy pivarate, Organic peroxide, the α such as 3,3,5-trimethyl acetyl base peroxide, the azo compounds such as α '-azodiisobutyronitrile Thing or Ammonium persulfate., potassium peroxydisulfate etc..
Binding agent for the present invention is preferably in the manufacturing process of binding agent, divides through removing binding agent The binding agent dissipating the granular metal removal step of granular metal contained in liquid and obtain.Glue by making The content of granular metal composition contained in mixture is below 10ppm, is possible to prevent in perforated membrane slurry Between polymer over time through and there is metal ion crosslinked, and then can prevent viscosity from rising.Additionally, The hidden danger that the self discharge that dissolving when secondary cell generation internal short-circuit and charging, precipitation cause increases is few, The cycle characteristics of battery and safety improve.
For above-mentioned granular metal removal step removes from binding agent dispersion liquid granular metal The method divided is not particularly limited.Such as can enumerate: filter by utilizing filter to carry out and remove Method, the method carrying out removing by vibrosieve, the method carrying out removing by centrifugation, pass through magnetic Power carries out the method etc. removed.Wherein, it is metal ingredient owing to removing object, the most preferably passes through magnetic force The method carrying out removing.As the method carrying out removing by magnetic force, as long as metal ingredient can be removed Method be just not particularly limited, if considering productivity and removing efficiency, the most preferably by binding agent Manufacture configuration magnetic filter in line to remove.
In the manufacturing process for the binding agent of the present invention, the dispersant used in above-mentioned polymerization can To be the dispersant used in common synthesis, as concrete example, can illustrate: detergent alkylate The benzene sulfonates such as sodium sulfonate, dodecylphenyl ether sulfonic acid sodium；Sodium lauryl sulfate, myristyl sulfate The alkyl sulfates such as sodium；The 2-Sulfosuccinic acids such as dioctyl sodium sulphosuccinate, dihexyl sodium sulfosuccinate Salt；The soaps such as lauric acid acid sodium；Sodium laureth sulfate salt, ethylene nonyl benzene The ethoxy sulfates such as base ether sodium sulfate salt；Paraffin sulfonate；Alkyl ether phosphates ester sodium salt；Polyoxyethylene Nonylplenyl ether, polyoxyethylene sorbitol acid anhydride Lauryl Ester, polyox-yethylene-polyoxypropylene block copolymer Deng non-ionic emulsifier；Gelatin, maleic anhydride-styrene copolymers, polyvinyl pyrrolidone, poly- The water soluble polymers etc. such as the polyvinyl alcohol of sodium acrylate, the degree of polymerization more than 700 and saponification degree more than 75%, These may be used alone, or two or more kinds may be used in combination.Wherein, preferred detergent alkylate sulphur The acid benzene sulfonate such as sodium, dodecylphenyl ether sulfonic acid sodium；Sodium lauryl sulfate, sodium tetradecyl sulfate Deng alkyl sulfate, from the standpoint of oxidative resistance is excellent, further preferred dodecylbenzene sodium sulfonate, The benzene sulfonates such as dodecylphenyl ether sulfonic acid sodium.The addition of dispersant can at random set, relatively In monomer total amount 100 mass parts, usually about 0.01～10 mass parts.
PH when binding agent for the present invention is scattered in disperse medium is preferably 5～13, more preferably 5～12, most preferably 10～12.By making the pH of binding agent be above-mentioned scope, the preservation of binding agent is stable Property improve, and then, mechanical stability improve.
The pH adjusting agent of the pH adjusting binding agent can illustrate: Lithium hydrate, sodium hydroxide, hydroxide The alkaline earth oxides such as the alkali metal hydroxides such as potassium, calcium hydroxide, magnesium hydroxide, barium hydroxide, Aluminium hydroxide etc. belong to the hydroxide of the metal of group III A in long period table (the 13rd race of the periodic table of elements) The hydroxide such as thing；The alkaline earth metal carbonates such as the alkali carbonate such as sodium carbonate, potassium carbonate, magnesium carbonate In carbonate etc.；As organic amine, can enumerate: the alkyl amines such as ethylamine, diethylamine, propyl group amine； The alcaminess such as single carbinolamine, monoethanolamine, single Propanolamine；The Ammonias etc. such as ammonia.Wherein, from caking property And from the viewpoint of operability, preferred alkali metal hydroxide, particularly preferred sodium hydroxide, potassium hydroxide, Lithium hydrate.
In every 100 mass % of total solid composition of perforated membrane slurry, binding agent is preferably containing ratio 0.5～20 mass %, more preferably 0.5～10 mass %, particularly preferably 1～5 mass %.Many by making In every 100 mass % of total solid composition of pore membrane slurry binding agent containing ratio in above-mentioned scope, permissible Prevent non-conductive organic granular described later from departing from (powder falling) from the perforated membrane of the present invention, make the softness of perforated membrane Property and use this perforated membrane secondary cell cycle characteristics improve.
(non-conductive organic granular)
Non-conductive organic granular for the present invention has can be with the heat cross-linking group of above-mentioned binding agent The functional group of crosslinking.In the present invention, being had by use can be with the crosslinking of above-mentioned heat cross-linking group The non-conductive organic granular of functional group, that can improve with the heat cross-linking group in above-mentioned binding agent is anti- Ying Xing, therefore can improve the dispersibility of non-conductive organic granular in perforated membrane slurry.
In the non-conductive organic granular of the present invention, it is possible to the sense of heat cross-linking group crosslinking Group is preferably hydrophilic radical, specifically can enumerate: carboxyl, sulfonic group, hydroxyl, phosphate etc..Its In, due to non-conductive with when the reactive height of the heat cross-linking group in binding agent, manufacture perforated membrane slurry Property organic granular dispersibility high, therefore preferably sulfonic group or phosphate, most preferably sulfonic group.By The list with the functional group that can cross-link is used with heat cross-linking group when manufacturing non-conductive organic granular Body, can import this functional group in non-conductive organic granular.
As having the monomer of carboxyl, can enumerate: monocarboxylic acid, dicarboxylic acids, the acid of dicarboxylic acids Acid anhydride and their derivant etc..
As monocarboxylic acid, can enumerate: acrylic acid, methacrylic acid .beta.-methylacrylic acid, 2-ethyl propylene Acid, iso-crotonic acid, α-acetoxypropen acid, β-trans-aryloxy group acrylic acid, α-chloro-β-E-methoxyl group Acrylic acid, β-diaminourea acrylic acid etc..
As dicarboxylic acids, can enumerate: maleic acid, fumaric acid, itaconic acid, citraconic acid, two Citraconic acid, phenyl maleic acid, chloromaleic acid, dichloromaleic acid and fluoro maleic acid etc..
As the anhydride of dicarboxylic acids, can enumerate: maleic anhydride, acrylic anhydride, methyl maleic anhydride, Dimethyl maleic anhydride etc..
As dicarboxylic acid derivatives, can enumerate: methyl allyl ester, maleic acid diphenyl ester, Maleic acid nonyl ester, maleic acid ester in the last of the ten Heavenly stems, maleic acid dodecyl ester, maleic acid stearyl and Malaysia The maleates such as acid fluoroalkyl.
As having sulfonic monomer, can enumerate: vinyl sulfonic acid, methyl ethylene sulfonic acid, (first Base) allyl sulphonic acid, styrene sulfonic acid, (methyl) acrylic acid-2-sulfonic acid, 2-acrylamide-2-methyl Propane sulfonic acid, 3-allyloxy-2-hydroxy-propanesulfonic acid etc..
As having the monomer of hydroxyl, can enumerate: (methyl) allyl alcohol, 3-butene-1-ol, 5-hexene The ethylene unsaturated alcohols such as-1-alcohol；2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, metering system Acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, maleic acid two-2-hydroxy methacrylate, maleic acid two-4- The alkanol esters of the ethylene unsaturated carboxylic acids such as hydroxybutyl, itaconic acid two-2-hydroxy propyl ester；Formula CH2 =CR1-COO-(CnH2nO)m-H (m represent 2～9 integer, n represent the integer of 2～4, R1Represent hydrogen Or methyl) shown in poly alkylene glycol and (methyl) acrylic acid formed esters；2-hydroxyethyl-2 '-(methyl) Acryloxy phthalic acid ester, 2-hydroxyethyl-2 ' the binary carboxylic such as-(methyl) acryloxy succinate List (methyl) esters of acrylic acid of the dihydroxy ester of acid；2-hydroxyethyl vinyl ether, 2-hydroxypropyl ethylene The vinyl ethers such as base ether；(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- The alkylenes such as hydroxybutyl ether, (methyl) pi-allyl-4-hydroxybutyl ether, (methyl) pi-allyl-6-hydroxyl hexyl ether List (methyl) allyl ether series of base glycol；Diethylene glycol list (methyl) allyl ether, dipropylene glycol list (methyl) The polyoxyalkylene glycols such as allyl ether (methyl) monoallyl ethers；Glycerol list (methyl) allyl ether, (gathering) alkylenes such as (methyl) pi-allyl-2-chloro-3-hydroxyl propyl ether, (methyl) pi-allyl-2-hydroxyl-3-chloropropyl ether The halogen of base glycol and list (methyl) allyl ether of hydroxyl substituent；Acetaminol, isoeugenol etc. are many List (methyl) allyl ether of unit's phenol and halogen substituents thereof；(methyl) pi-allyl-2-hydroxyethyl thioether, (first Base) (methyl) allyl sulfide ethers etc. of the aklylene glycol such as pi-allyl-2-hydroxypropyl thioether.
As having the monomer of phosphate, can enumerate: phosphoric acid-2-(methyl) acryloyloxyethyl ester, phosphorus Acid methyl-2-(methyl) acryloyloxyethyl ester, ethyl-(methyl) acryloyloxyethyl ester etc..
Preferably with respect to non-conductive organic granular, the content of the functional group in non-conductive organic granular is 0.008～0.240mmol/g, more preferably 0.014～0.14mmol/g.By making non-conductive organic granular In amount of functional groups in above-mentioned scope, functional group in non-conductive organic granular can be kept fully Mobility, therefore can improve the reactivity with binding agent.It is as a result, it is possible to increase porous film strength.
Non-conductive organic granular preferably further contains the polymerized unit of divinylbenzene.Non-conductive In total monomer weight in organic granular, the polymerized unit of divinylbenzene be preferably 20～80 containing ratio Quality %, more preferably 25～70 mass %, particularly preferably 30～60 mass %.Non-conductive by making Containing the polymerized unit of divinylbenzene in organic granular, the crosslink density of electric conductivity organic granular uprises, Therefore, the thermostability of non-conductive organic granular improves, and the reliability of gained secondary cell perforated membrane also carries High.
Non-conductive organic granular preferably further contains the polymerized unit of vinyl xylene, ethyl vinyl benzene.Non-conductive In total monomer weight in property organic granular, being preferably containing ratio of the polymerized unit of vinyl xylene, ethyl vinyl benzene 3.2～48 mass %, more preferably 10～40 mass %.By making in non-conductive organic granular containing ethyl The polymerized unit of vinyl benzene, becomes good with the caking property of above-mentioned binding agent, can prevent from non-conductive having Machine granule departs from (powder falling) from secondary cell perforated membrane.It addition, the flexibility of gained secondary cell perforated membrane becomes Obtain well.And then, the situation of electrode for secondary battery is made at this secondary cell perforated membrane of electrode superimposed layer Under, it is also possible to prevent the disengaging (powder falling) of electrode active material.Its result, uses this secondary cell perforated membrane Secondary cell demonstrate excellence cycle characteristics.
The polymerized unit of divinylbenzene contained in non-conductive organic granular and gathering of vinyl xylene, ethyl vinyl benzene The content ratio (divinylbenzene/vinyl xylene, ethyl vinyl benzene) closing unit is preferably 1.0～5.25, more preferably 1.25～5.00, particularly preferably 1.25～4.75.By making divinyl contained in non-conductive organic granular The content of the polymerized unit of base benzene and the polymerized unit of vinyl xylene, ethyl vinyl benzene is than for above-mentioned scope, non-conductive The crosslink density of organic granular uprises, and therefore, the thermostability of non-conductive organic granular improves.Its result, The flexibility of gained secondary cell perforated membrane and intensity improve.It addition, non-conductive organic granular can be prevented (powder falling) is departed from, meanwhile, in the feelings using this perforated membrane to make electrode for secondary battery from secondary cell perforated membrane Under condition, it is possible to prevent the disengaging (powder falling) of electrode active material, therefore, uses the secondary cell of this perforated membrane Demonstrate the cycle characteristics of excellence.
In addition to above-mentioned 2 kinds of polymerized units, can also be containing arbitrarily polymerization in non-conductive organic granular Unit.As the monomer (any monomer) of any polymerized unit of composition, can enumerate: polynary (methyl) propylene Ester compound, aromatic mono-vinyl based compound, acrylonitrile compound, (methyl) acrylate monomer, Conjugate diene monomer, vinyl ester compound, alpha-olefin compound, cationic monomer, containing epoxy radicals Monomer, amide-containing monomer.Non-conductive organic granular can contain these monomers of more than two kinds.
As polynary (methyl) acrylate compounds, can enumerate: polyethyleneglycol diacrylate, 1,3- Butanediol diacrylate, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, polypropylene glycol Diacrylate, 2,2 '-bis-(4-acryloxy propoxyphenyl) propane, 2,2 '-bis-(4-acryloxies two Ethoxyl phenenyl) diacrylate compounds such as propane；Trimethylolpropane trimethacrylate, trihydroxy methyl The triacrylate compound such as ethane triacrylate, tetramethylol methane triacrylate；Tetra methylol The tetra-acrylate compound such as methane tetraacrylate；Ethylene glycol dimethacrylate, diethylene glycol two Methacrylate, TEGDMA, polyethylene glycol dimethacrylate, 1,3- Butanediol dimethylacrylate, 1,4-butanediol dimethylacrylate, 1,6-HD dimethyl allene Acid esters, neopentylglycol dimethacrylate, dipropylene, polypropylene glycol diformazan The dimethylacrylates such as base acrylate, 2,2 '-bis-(4-methacryloxy diethoxy phenyl) propane Compound；Trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methacrylate etc. three Methacrylate compound etc..Wherein, ethylene glycol dimethacrylate or trihydroxy methyl are preferably used Propane trimethyl acrylic ester.
As aromatic mono-vinyl based compound, can enumerate: styrene, α-methyl styrene, fluoro Styrene, 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 '-dimethyl amino ethyl ester etc..
As methacrylate monomer, can enumerate: butyl methacrylate, methacrylic acid 2-second The own ester of base, methyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid N, N '-dimethyl Amino ethyl ester etc..
As conjugate diene monomer, can enumerate: butadiene, isoprene etc..
As vinyl ester compound, can enumerate: vinyl acetate etc..
As alpha-olefin compound, can enumerate: 4-methyl-1-pentene etc..
As cationic monomer, can enumerate: (methyl) acrylate, (methyl) third Olefin(e) acid dimethylamino propyl ester etc..
As containing epoxy based monomers, can enumerate: glycidyl acrylate, Glycidyl methacrylate are sweet Grease etc..
As amide-containing monomer, can enumerate: acrylamide, Methacrylamide, N-methylol third Acrylamide, N-methylol methacrylamide etc..
Above-mentioned any monomer can be used alone wantonly a kind or two or more be applied in combination.Above-mentioned arbitrarily In monomer, particularly from the reactivity of divinylbenzene and vinyl xylene, ethyl vinyl benzene from the viewpoint of, preferably Styrene, methyl methacrylate or combinations thereof.
In total monomer weight in non-conductive organic granular, any polymerized unit preferred containing ratio It is 3～80 mass %, more preferably 4～70 mass %, particularly preferably 5～60 mass %.Particularly exist Containing styrene and/or methyl methacrylate as any monomer in the case of, non-conductive have to constitute On the basis of the monomer total amount of machine granule, it preferably contains ratio is 4.5～76.5 mass %.Containing benzene In the case of both ethylene and methyl methacrylate, preferably their total amount is within the range.Pass through Make styrene and/or methyl methacrylate is below 76.5 mass % containing ratio, can improve non-leading The electrically thermostability of organic granular, it is thus possible to improve the thermostability of perforated membrane, and then height can be reduced The generation of the lower battery short circuit of temperature.On the other hand, by making containing of styrene and/or methyl methacrylate Ratio is more than 4.5 mass %, is possible to prevent the dispersibility of non-conductive organic granular to reduce, can improve Porous film strength, and, it is also possible to obtain film uniformity.
(manufacture method of non-conductive organic granular)
The manufacture method of non-conductive organic granular is not particularly limited, and can enumerate following method: by structure The above-mentioned monomer becoming non-conductive organic granular and other any composition used as desired dissolve or divide Dissipate in disperse medium, and utilize emulsion polymerization or soap-free polymerization method to be polymerized in this dispersion liquid.
In emulsion is polymerized, from the standpoint of obtaining desired particle diameter and average circularity, preferably will be poly- Conjunction is divided into multiple stage to carry out.Such as, by first the one of the monomer of non-conductive organic granular will be constituted Part carries out polymerization to form seeding polymerization composition granule, it follows that make this seeding polymerization composition granule absorb it Its monomer, is polymerized in this condition, can manufacture non-conductive organic granular (seeded polymerization).Enter And, when forming seeding polymerization composition granule, polymerization can be further divided into multiple stage to be carried out.
More specifically, the part formation of the monomer constituting non-conductive organic granular can such as be used Seeding polymerization composition granule A, uses this seeding polymerization composition granule A and constitutes non-conductive organic granular Other monomer forms the seeding polymerization composition granule B with bigger particle diameter, then, uses this seeding polymerization Composition granule B and constitute remaining monomer of non-conductive organic granular and use as desired other Meaning composition forms the non-conductive organic granular with bigger particle diameter.So, anti-by by 2 stages Should form seeding polymerization composition granule, then form non-conductive organic granular further, having can be stably The advantage obtaining desired particle diameter and average circularity.Now, the list of non-conductive organic granular will be constituted In body have can with heat cross-linking group crosslinking functional group monomer part or all of (preferably All) use when forming seeding polymerization composition granule A and seeding polymerization composition granule B, it can be ensured that granule steady Qualitative, therefore preferably.It addition, now, use the styrene as any monomer as being used for forming seed The monomer of polymer beads A, when forming seeding polymerization composition granule B and non-conductive organic granular, can Guarantee monomer absorbability in seeding polymerization composition granule, therefore preferably.
Owing to also including the situation being divided into multiple stage to carry out being polymerized as above, therefore, constitute non-leading Electrically the monomer of organic granular is when polymerization, it is also possible to being formed without its whole monomers becomes the state of mixture. In the case of polymerization is divided into multiple stage to carry out, in the non-conductive organic granular finally given, come Preferably meet from the composition of monomer of the polymerized unit constituting non-conductive organic granular that above-mentioned composition is non-to be led The electrically ratio of components of the monomer of organic granular.
The medium used in polymerization as the monomer constituting non-conductive organic granular, can enumerate: Water, organic solvent and their mixture.As organic solvent, it is possible to use be combined into for radical polymerization Nonactive and that monomer will not be hindered to be polymerized solvent.As the concrete example of organic solvent, can enumerate: first Alcohols, phthalic acid dibutyl ester, the dioctyl phthalates such as alcohol, ethanol, propanol, Hexalin, capryl alcohol In the ketone such as esters, Ketohexamethylene and they mixture.Preferably use the aqueous mediums such as water as dividing Dispersion media carries out the emulsion polymerization as polymerization.
When making seeding polymerization composition granule and monomer react, the ratio of their amount with monomer relative to seed The use gauge of polymer beads 1 mass parts, preferably 2～19 mass parts, more preferably 3～16 mass Part, more preferably 4～12 mass parts.By making monomer relative to seeding polymerization composition granule 1 mass parts Usage amount be more than 2 mass parts, can improve the non-conductive organic granular obtained mechanical strength and Thermostability.It addition, be 19 matter by making monomer relative to the usage amount of seeding polymerization composition granule 1 mass parts Below amount part, monomer can be made to be efficiently absorbed in seeding polymerization composition granule, therefore, it can not planted The amount of monomer that sub-polymer beads absorbs remains less scope.Further, since can carry out well The control of the particle diameter of non-conductive organic granular, accordingly it is possible to prevent have thick of wide particle diameter distribution Grain and the generation of substantial amounts of molecule.
As the concrete operations of polymerization, have and once put into relative to the aqueous dispersion of seeding polymerization composition granule The method of monomer, carry out polymerization while the method for adding monomer in batch or continuously.Preferably in polymerization Seeding polymerization composition granule is made to absorb before being initiated and seeding polymerization composition granule substantially producing crosslinking single Body.
If adding monomer after the mid-term of polymerization, then do not absorbed by seeding polymerization composition granule due to monomer, Therefore may result in molecule to produce in a large number and make polymerization stability be deteriorated, it is impossible to maintain polyreaction. It is therefore preferable that relative to seeding polymerization composition granule, add whole monomers before polymerization causes or in polymerization Conversion ratio reaches to terminate before about 30% the interpolation of whole monomers.Particularly preferably at seed before polymerization causes The aqueous dispersion of polymer beads add monomer and is stirred, making seeding polymerization composition granule absorb institute Polymerization is caused after stating monomer.
In the reaction system of polymerization, except constitute the monomer of non-conductive organic granular and disperse medium with Outward, it is also possible to add any composition.Specifically, can add polymerization initiator, surfactant, The compositions such as suspension protective agent.As polymerization initiator, it is possible to 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 by above-mentioned water The oxidation that soluble initiator or the reducing agent combination such as oil-soluble initiator described later and sodium sulfite are formed is also Former series initiators.It addition, as oil-soluble radical polymerization initiator, can enumerate: benzoyl peroxide Formyl, α, α '-azodiisobutyronitrile, peroxide-2-ethyl hexanoic acid tert-butyl, 3,5,5-trimethyl acetyl base mistake Oxide etc..In oil-soluble radical polymerization initiator, preferably use peroxidating-2 ethyl hexanoic acid uncle Butyl ester.It should be noted that in the polymerization, if adding potassium dichromate, iron chloride, hydroquinone on a small quantity Etc. water miscible polymerization inhibitor, then can suppress the generation of molecule, therefore preferably.
As surfactant, it is possible to use common surfactant, such as dodecyl can be illustrated Benzene sulfonic acid sodium salt, sodium lauryl sulfate, dialkyl sodium sulfosuccinate, the moon such as formaldehyde condensation products of LOMAR PWA EINECS 246-676-2 Ionization series emulsifying agent.In addition it is also possible to it is hard to be applied in combination ethylene nonyl phenyl ether, polyethyleneglycol The nonionic surfactant such as matter acid esters, sorbitan list hard acid esters.As the guarantor that preferably suspends Protect agent, can enumerate: polyvinyl alcohol, carboxymethyl cellulose, sodium polyacrylate or micropowder inorganic chemical Thing etc..
(character of non-conductive organic granular)
For the present invention non-conductive organic granular be shaped as spherical, needle-like, bar-shaped, fusiform, Tabulars etc., are not particularly limited, but the most spherical, needle-like, fusiform.It addition, as non-conductive Organic granular, it is possible to use porous particles.Every 100 mass % of total solid composition of perforated membrane slurry In non-conductive organic granular be preferably 70～97 mass % containing ratio, more preferably 80～95 mass %, Particularly preferably 85～95 mass %.By non-in every 100 mass % of total solid composition that make perforated membrane slurry Electric conductivity organic granular is above-mentioned scope containing ratio, can obtain showing the perforated membrane of high thermal stability. And it is possible to be inhibited, non-conductive organic granular departs from (powder falling) from perforated membrane and display high intensity is many Pore membrane, is possible to prevent the reduction of the battery behaviors such as cycle characteristics simultaneously.
From perforated membrane is given thermostability, improve electrode for secondary battery described later and secondary battery separator can From the viewpoint of property, the most non-conductive organic granular has high-fire resistance.Specifically, by heat Balance is analyzed when heating with programming rate 10 DEG C/min under nitrogen atmosphere, the loss of weight of non-conductive organic granular Ratio reaches the temperature of 10 mass % and is preferably more than 250 DEG C, more preferably more than 300 DEG C, the most excellent Elect more than 360 DEG C as.On the other hand, the upper limit of this temperature is not particularly limited, and can be such as 450 DEG C Below.
In the present invention, as non-conductive organic granular, the content that metal impurities are preferably used is The non-conductive organic granular of below 100ppm.Metal impurities or metal ion is more contained if using Non-conductive organic granular, then in perforated membrane slurry, above-mentioned metal impurities or digestion of metallic ion, its The polymer in perforated membrane slurry and ionomer, perforated membrane slurry is caused to condense, its result is many The porous of pore membrane reduces.Accordingly, it is possible to cause the multiplying power property using the secondary cell of this perforated membrane (defeated Go out characteristic) it is deteriorated.As above-mentioned metal, especially, least preferred containing Ca, Co, Cu, Fe, Mg, Ni, Zn and Cr etc..Accordingly, as the tenor in non-conductive organic granular, with these metals The total amount meter of ion, preferably below 100ppm, more preferably below 50ppm.Above-mentioned content The fewest, more it is difficult to cause the deterioration of battery behavior.Here described " metal impurities " refer to non-conductive Metal simple-substance beyond organic granular or metal ion.Containing of metal impurities in non-conductive organic granular Amount can use ICP (inductively coupled plasma (Inductively Coupled Plasma)) to be measured.
Mean diameter for the non-conductive organic granular of the present invention is preferably 0.1～2 μm, more preferably 0.1～1 μm, particularly preferably 0.1～0.8 μm.It is upper by the mean diameter making non-conductive organic granular State scope, be easily controlled the dispersity of perforated membrane slurry, therefore, easily produce homogenizing have to Determine the perforated membrane of thickness.It is additionally possible to suppress particles filled rate uprises in perforated membrane, therefore, it can press down Ionic conductivity in perforated membrane processed reduces, such that it is able to realize excellent cycle characteristics.If making non-conductive The scope that mean diameter is 0.1～0.8 μm of property granule, then the easy degree disperse, being coated with, space Controlling is excellent, therefore particularly preferably.Mean diameter can be obtained as follows: carries out electron microscope observation, For more than 100 granules, the longest edge of its particle image is set to a, minor face is set to b, calculates (a+b)/2, its meansigma methods obtain mean diameter.
Average circularity for the non-conductive organic granular of the present invention is preferably 0.900～0.995, more excellent Elect 0.91～0.98 as, particularly preferably 0.92～0.97.By making the average circular of non-conductive organic granular Degree is above-mentioned scope, can moderately keep non-conductive organic granular contact area each other, therefore, Porous film strength and thermostability can be improved.It is as a result, it is possible to increase use the secondary electricity of this perforated membrane The reliability in pond.
It addition, for the BET specific surface area for the non-conductive organic granular of the present invention, from suppression From the viewpoint of the cohesion of non-conductive organic granular and the mobility of optimization perforated membrane slurry, specifically, It is preferably 0.9～200m2/ g, more preferably 1.5～150m2/g。
The particle diameter distribution preferably 1.00～1.4 of non-conductive organic granular, more preferably 1.00～1.3, especially It is preferably 1.00～1.2.By making the particle diameter of non-conductive organic granular be distributed as above-mentioned scope, can make non- Keep given space between electric conductivity organic granular, therefore, it can suppress the present invention secondary cell in by Movement in lithium is obstructed and is caused resistance to increase.It should be noted that the particle diameter of non-conductive organic granular Distribution can be at the laser diffraction refraction particle size distribution device using Beckman Co., Ltd. to manufacture (LS230) after carrying out particle size determination, by the ratio V/N of volume average particle size V obtained and number average bead diameter N Obtain.
(solvent)
As the solvent for perforated membrane slurry, it is possible to use any solvent in water and organic solvent.Make For organic solvent, can enumerate: the annular aliphatic hydro carbons such as Pentamethylene., hexamethylene；Toluene, dimethylbenzene, Ethylo benzenes etc. are aromatic hydrocarbon；Acetone, butanone, diisopropyl ketone, Ketohexamethylene, hexahydrotoluene, The ketones such as ethyl cyclohexane；The chlorine system aliphatic hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride；Ethyl acetate, The esters such as butyl acetate, gamma-butyrolacton, 6-caprolactone；The nitrile such as acetonitrile, propionitrile；Oxolane, second two The ethers such as diethylene glycol diethyl ether: the alcohols such as methanol, ethanol, isopropanol, ethylene glycol, glycol monoethyl ether；N- The amide-type such as methyl pyrrolidone, N,N-dimethylformamide.
These solvents can be used alone, it is also possible to two or more in them is mixed mixed solvent Use.Wherein, it is molten that the excellent dispersion of the most non-conductive granule, boiling point be low and volatility is high Agent, can remove under short time and low temperature, therefore preferably.Specifically, preferably acetone, toluene, ring Hexanone, Pentamethylene., oxolane, hexamethylene, dimethylbenzene, water or N-Methyl pyrrolidone or it Mixed solvent.
(any composition)
In perforated membrane slurry in addition to mentioned component (binding agent, non-conductive organic granular and solvent), also may be used To contain any composition further.As this any composition, can enumerate: inorganic particle, dispersant, Binding agent, viscosifier, defoamer beyond levelling agent, antioxidant, above-mentioned binding agent and there is electricity Solution liquid decomposes the compositions such as the electrolysis additive of the functions such as suppression.As long as these compositions will not be to cell reaction Impact and be just not particularly limited.
As inorganic particle, it is possible to use such as aluminium oxide, silicon oxide, magnesium oxide, titanium oxide, nitridation The various inorganic particles such as aluminum, calcium fluoride, barium fluoride, Talcum, montmorillonite.The total solid of perforated membrane slurry In every 100 mass % of composition, inorganic particle is below 20 mass % containing ratio, more preferably 10 mass Below %.If inorganic particle is this scope containing ratio, then can obtain the much higher pore membrane of intensity.
As dispersant, Exemplary anions compound, cationic compound, nonionic chemical combination Thing, macromolecular compound.Dispersant can select according to the non-conductive organic granular used.Porous In every 100 mass % of total solid composition of film slurry dispersant containing ratio preferably will not be special to battery The scope that property impacts, below specially 10 mass %.If dispersant is this scope containing ratio, Then the screening characteristics of the perforated membrane slurry of the present invention is good, can obtain uniform perforated membrane.
As levelling agent, can enumerate: alkyl-based surfactant, silicone surfactant, fluorine class The surfactants such as surfactant, metal class surfactant.The total solid composition of perforated membrane slurry is every In 100 mass % surfactant containing ratio preferably in the scope that battery behavior will not be impacted, It is specially below 10 mass %.By mixing above-mentioned surfactant, it is possible to prevent the porous of the present invention Produce when film slurry is coated on given matrix material and repel (は じ I), make the flatness of perforated membrane improve.
As antioxidant, can enumerate: phenolic compound, hydroquinone compound, organic phosphorus compound, Sulphur compound, phenylenediamine compound, polymer-type phenolic compound etc..Polymer-type phenols chemical combination Thing is the polymer in intramolecular with phenol structure, and preferably to use weight average molecular weight be 200～1000, excellent Select the polymer-type phenolic compound of 600～700.Every 100 mass % of total solid composition of perforated membrane slurry Middle antioxidant containing ratio preferably in the scope that battery behavior will not be impacted, specially 10 matter Amount below %.If antioxidant is this scope containing ratio, then the cycle life of battery is excellent.
As the binding agent beyond above-mentioned binding agent, it is possible to use used in binding agent for electrode described later Politef (PTFE), Kynoar (PVDF), polyacrylic acid derivative, polyacrylonitrile derive Thing, soft polymer etc..In every 100 mass % of total solid composition of perforated membrane slurry above-mentioned binding agent with Outer binding agent is below 10 mass % containing ratio.If binding agent is this scope containing ratio, then The perforated membrane of the present invention and the adaptation of electrode active material layer described later and organic dividing plate are good.
As viscosifier, can enumerate: carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose etc. Cellulosic polymer and their ammonium salt and alkali metal salt；(modified) poly-(methyl) acrylic acid and they Ammonium salt and alkali metal salt；(modified) polyvinyl alcohol, acrylic acid or acrylates and the copolymer of vinyl alcohol, The polyvinyl alcohols such as the copolymer of maleic anhydride or maleic acid or fumaric acid and vinyl alcohol；Polyethylene Glycol, Poly(ethylene oxide), polyvinyl pyrrolidone, modified polyacrylic acid, Oxytarch, starch phosphate, cheese Albumen, various modified starch, acrylonitrile-butadiene copolymer hydride etc..The total solid of perforated membrane slurry In every 100 mass % of composition viscosifier containing ratio preferably at the model that battery behavior will not be impacted Enclose, below specially 10 mass %.If viscosifier are this scope containing ratio, then the porous of the present invention The screening characteristics of film slurry and the perforated membrane of the present invention and electrode active material layer described later and organic dividing plate Adaptation good.In the present invention, " (modified) is poly-" refers to " unmodified poly-" or " modified poly-", " (first Base) acrylic acid " refer to " acrylic acid " or " methacrylic acid ".
As defoamer, metal soap, polysiloxane-based, polyethers, higher alcohols, perfluor can be used Alkyls etc..In every 100 mass % of total solid composition of perforated membrane slurry, defoamer is preferred containing ratio Below the scope that battery behavior will not be impacted, specially 10 mass %.By mixture foam killer, The froth breaking operation of binding agent can be shortened.
Electrolysis additive can use the carbonic acid in electrode slurry described later and used in electrolyte sub- Vinyl acetate etc..In every 100 mass % of total solid composition of perforated membrane slurry electrolysis additive containing than Rate is preferably below the scope that will not impact battery behavior, specially 10 mass %.By mixing Electrolysis additive, the cycle life of battery is excellent.
Furthermore, it is possible to enumerate: nanoparticles such as aerosil, gaseous oxidation aluminum.By in mixing State nanoparticle, the thixotropy of perforated membrane slurry can be controlled, and then, can improve thus obtained many The levelability of pore membrane.
Above-mentioned arbitrary composition containing ratio in every 100 mass % of total solid composition of perforated membrane slurry Summation is preferably below 40 mass %, below more preferably 20 mass %.But, above-mentioned binding agent, The summation of non-conductive organic granular and arbitrarily composition (wherein, not including binding agent) is less than 100 mass % In the case of, can by using the binding agent as any composition containing ratio convenient increment, obtain group Compound.
As long as the solid component concentration of perforated membrane slurry be can carry out the coating of this slurry, the degree of dipping and The viscosity with mobility is just not particularly limited, it is however generally that be about 10～50 mass %.
Composition beyond solid constituent is the composition volatilized by drying process, in addition to above-mentioned solvent, Also include such as dissolving in binding agent and the preparation of non-conductive organic granular and when adding or disperseing theirs Medium.
The manufacture method of secondary cell perforated membrane slurry is not particularly limited, can by mix above-mentioned binding agent, Non-conductive organic granular, solvent and any composition added as desired manufacture.In the present invention, By use mentioned component (binding agent, non-conductive organic granular, solvent and add as desired appoint Meaning composition), no matter mixed method and order by merging, all can obtain high degree of dispersion has non-conductive The perforated membrane slurry of grain.Mixing arrangement can use the mixing arrangement phase with the manufacture for above-mentioned binding agent Same mixing arrangement.Wherein, particularly preferably use can apply high dispersive and shear ball mill, roller mill, Fill mixer (Fill-mix, Off ィ Le ミ ッ Network ス) contour dispersal device.
From the viewpoint of even application, slurry ageing stability, the viscosity of perforated membrane slurry is preferably 10～10,000mPa s, more preferably 50～500mPa s.Above-mentioned viscosity exists for using Brookfield viscometer 25 DEG C, value when measuring under conditions of rotating speed 60rpm.
Can be with the functional group of heat cross-linking group crosslinking in non-conductive organic granular in perforated membrane slurry (can be with the official of this heat cross-linking group crosslinking relative to the weight ratio of the heat cross-linking group in binding agent Energy group/heat cross-linking group) preferably 0.2～3, more preferably 0.3～3, particularly preferably 0.3～2.If should Weight ratio (can be with the functional group/heat cross-linking group of this heat cross-linking group crosslinking) is above-mentioned scope, then Being possible to prevent the gelation of perforated membrane slurry, the screening characteristics making perforated membrane slurry is good, therefore, and perforated membrane Flexibility and intensity improve.
(2) secondary cell perforated membrane
The secondary cell perforated membrane (being the most also denoted as " perforated membrane ") of the present invention is by above-mentioned secondary cell porous Film slurry is formed as membranaceous and is dried forming.
It addition, the perforated membrane of the present invention is comprising the polymerization list of the vinyl monomer with heat cross-linking group The binding agent of unit and have can be with functional group non-conductive organic of this heat cross-linking group crosslinking There is between granule cross-linked structure.Described cross-linked structure is that binding agent and non-conductive organic granular are by changing The molecular structure that key carries out being bonded and formed.
Perforated membrane is stacked on organic dividing plate, electrode use or uses as organic dividing plate itself.
<manufacture method of secondary cell perforated membrane>
As manufacturing the method for perforated membrane of the present invention, can enumerate: (I) will be containing above-mentioned binding agent, non- The perforated membrane slurry of electric conductivity organic granular, solvent and any composition (is just being coated on given matrix material Pole, negative pole or organic dividing plate) on, the method being then dried；(II) will containing above-mentioned binding agent, non-lead Electrically organic granular, solvent and arbitrarily composition perforated membrane impregnating slurry matrix material (positive pole, negative pole or Organic dividing plate) in after, the method that it is dried；(III) will be containing above-mentioned binding agent, non-conductive The perforated membrane slurry of organic granular, solvent and any composition is coated on stripping film and carries out film forming, and will To perforated membrane be transferred in the method on given matrix material (positive pole, negative pole or organic dividing plate).Wherein, (I) perforated membrane slurry is coated on matrix material (positive pole, negative pole or organic dividing plate) side being then dried Method is easily controlled the thickness of perforated membrane, therefore most preferably.
The perforated membrane of the present invention can be by above-mentioned (I)～the method manufacture of (III), below, the manufacturer concrete to it Method illustrates.
In the method for (I), by perforated membrane slurry is coated on given matrix material (positive pole, negative pole or Organic dividing plate) go up and be dried the perforated membrane manufacturing the present invention.
The method that this slurry is coated on matrix material is not particularly limited, such as, can enumerate: scraper The methods such as rubbing method, inverse roller method, direct rolling method, intagliotype, squeezing and pressing method, spread coating.Wherein, from From the standpoint of available uniform perforated membrane, preferably intagliotype.
As drying means, can enumerate: utilize dry, the vacuum of such as warm air, hot blast, low wet wind The seasoning being dried, utilizing (far) infrared ray or electron beam etc. to irradiate.Baking temperature can be molten according to use The kind of agent changes.In order to completely remove solvent, such as, using the volatility such as N-Methyl pyrrolidone In the case of low solvent, preferably it is dried with under the drying machine of blast type high temperature more than 120 DEG C. On the contrary, in the case of using the solvent that volatility is high, it is also possible to do in a low temperature of below 100 DEG C Dry.When organic dividing plate described later forms perforated membrane, owing to needing not cause the contraction ground of organic dividing plate It is dried, it is therefore preferable that be dried in a low temperature of below 100 DEG C.
In the method for (II), by by perforated membrane impregnating slurry in matrix material (positive pole, negative pole or organic every Plate) in and be dried the perforated membrane manufacturing the present invention.This impregnating slurry is not had in the method for matrix material There is restriction especially, such as, can impregnate by carrying out dip coated with dip coater etc..
As drying means, the method identical with the drying means in the method for above-mentioned (I) can be enumerated.
In the method for (III), being coated on stripping film by perforated membrane slurry and carry out film forming, manufacture is formed at Perforated membrane on stripping film.Then, the perforated membrane obtained is transferred in matrix material (positive pole, negative pole or have Machine dividing plate) on.
As coating process, the method identical with the coating process in the method for above-mentioned (I) can be enumerated.Turn Impression method is not particularly limited.
For the perforated membrane obtained by the method for (I)～(III), it is also possible to then according to needs use moulding press, Roll squeezers etc. improve matrix material (positive pole, negative pole or organic dividing plate) by pressurized treatments and perforated membrane is close Conjunction property.But now, if excessively carrying out pressurized treatments, the voidage of perforated membrane is impaired the most sometimes, therefore, Suitably control pressure and pressing time.
The thickness of perforated membrane is not particularly limited, can be suitable according to the purposes of perforated membrane or application Setting, if the thinnest, then cannot form uniform film, on the contrary, if blocked up, then the monomer volume in battery is (heavy Amount) capacity (capacity) reduce, it is therefore preferable that 0.5～50 μm, more preferably 0.5～10 μm.
The perforated membrane of the present invention is at the surface filming of matrix material (positive pole, negative pole or organic dividing plate), the most excellent Select protecting film or the dividing plate making electrode active material layer described later.The perforated membrane of the present invention can be two The arbitrary surfaces film forming of the positive pole of primary cell, negative pole or organic dividing plate, it is also possible at positive pole, negative pole and have The whole upper film forming of machine dividing plate.
(3) electrode for secondary battery
As secondary cell, can enumerate: lithium rechargeable battery, nickel-hydrogen secondary cell etc..Wherein, Due to require most to improve safety and perforated membrane to import effect the highest, therefore preferred lithium rechargeable battery, Therefore, below the situation for lithium rechargeable battery is illustrated.
The electrode for secondary battery of the present invention contains collector body, is attached to this collector body and containing electrode activity thing Matter and the electrode active material layer of binding agent and be stacked on this electrode active material layer surface above-mentioned Secondary cell perforated membrane.That is, the electrode for secondary battery of the present invention is attached with on the current collector and comprises electrode active Property material and the electrode active material layer of binding agent for electrode, and at the surface stack of electrode active material layer There is above-mentioned secondary cell perforated membrane.
(electrode active material)
As long as the electrode active material used in electrode for lithium ion secondary battery can be by electrolysis Matter applies voltage reversibly embed or the active substance of deintercalate lithium ions, inorganic compound or have Machine compound all can use.
The electrode active material (positive active material) of lithium ion secondary battery positive electrode is roughly divided into by inorganic Active substance that compound is constituted and the active substance that is made up of organic compound.As by inorganic compound The positive active material constituted, can enumerate: the composite oxygen of transition metal oxide, lithium and transition metal Compound, transient metal sulfide etc..As above-mentioned transition metal, Fe, Co, Ni, Mn can be used Deng.As the concrete example of the inorganic compound used in positive active material, can enumerate: LiCoO2、 LiNiO2、LiMnO2、LiMn2O4、LiFePO4、LiFeVO4Deng lithium-contained composite metal oxide；TiS2、 TiS3, noncrystalline MoS2Deng transient metal sulfide；Cu2V2O3, noncrystalline V2O-P2O5、MoO3、 V2O5、V6O13Deng transition metal oxide.Can also be the Partial Elements in these compounds replaced after Obtained compound.As the positive active material being made up of organic compound, it is possible to use such as Polyacetylene, poly-to electroconductive polymers such as benzene.For the ferrum type oxide of poorly conductive, can be by making There is carbon source material when carrying out reduction roasting in it, is made into the electrode active material covered by material with carbon element Use.Additionally, these compounds after can also to be Partial Elements replaced obtained by compound.
Positive electrode active material for lithium ion secondary battery can also be above-mentioned inorganic compound and organic compound The mixture of thing.The particle diameter of positive active material can be according to the balance being formed arbitrarily between important document of battery And suitably select, but from the viewpoint of the battery behavior such as multiplying power property, cycle characteristics improves, 50% body The long-pending particle diameter of accumulation is usually 0.1～50 μm, preferably 1～20 μm.If 50% volume-cumulative particle diameter is this model Enclose, the secondary cell that charge/discharge capacity is big, and operation when manufacture electrode slurry and electrode can be obtained Easily.50% volume-cumulative particle diameter can be by obtaining by determination of laser diffraction particle size distribution.
As lithium ion secondary battery negative pole with electrode active material (negative electrode active material), such as, can lift Go out: the carbonaceous materials such as amorphous carbon, graphite, native graphite, carbonaceous mesophase spherules, pitch-based carbon fiber, The Electroconductivity of Conducting Polymers etc. such as coalescence benzene.It addition, as negative electrode active material, can use silicon, stannum, Metal or their alloy, the oxide of above-mentioned metal or alloy, the sulfate such as zinc, manganese, ferrum, nickel. Further, it is possible to use the lithium alloy such as lithium metal, Li-Al, Li-Bi-Cd, Li-Sn-Cd, lithium transition-metal Nitride, silicone etc..Electrode active material can also be used and be conducted electricity in surface attachment by mechanically modifying method Give the active substance of material.The particle diameter of negative electrode active material can be wanted according to other composition with battery Balance between part and suitably select, from battery behaviors such as initial efficiency, multiplying power property, cycle characteristics From the viewpoint of raising, 50% volume-cumulative particle diameter is usually 1～50 μm, is preferably 15～30 μm.
(binding agent for electrode)
In the present invention, electrode active material layer is in addition to electrode active material, containing binding agent (below, Also " binding agent for electrode " it is denoted as.).By containing binding agent for electrode, the electrode activity thing in electrode The caking property of matter layer improves, electrode roll around time etc. rise relative to the intensity of the power of this machinery in operation, It addition, the electrode active material layer in electrode becomes to be not easily disconnected from, therefore, the short circuit etc. that thing causes is departed from Danger diminish.
As binding agent for electrode, it is possible to use various resinous principles.Such as can use poly-second Alkene, politef (PTFE), Kynoar (PVDF), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), Polyacrylic acid derivative, HPAM Degraded Bacteria etc..These may be used alone, can also be used in combination 2 More than Zhong.Alternatively, it is also possible to the binding agent of the perforated membrane being used for the present invention is used as binding agent for electrode.
Further, it is also possible to use soft polymer exemplified below as binding agent for electrode.
Can enumerate:
Acrylic compounds soft polymer: butyl polyacrylate, polybutyl methacrylate, polymethyl Acid hydroxy methacrylate, polyacrylamide, polyacrylonitrile, n butyl acrylate styrene, acrylic acid fourth The propylene such as ester-acrylonitrile copolymer, butyl acrylate-acrylonitrile-glycidyl methacrylate copolymer Acid or the homopolymer of methacrylic acid derivative or they and the copolymerization that can be formed with the monomer of its copolymerization Thing；
Isobutylene type soft polymer: polyisobutylene, 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 (ABS) Copolymer, butadiene-styrene block copolymer, styrene butadiene styrene block copolymer (SBS), different Isoprene-styrene block copolymer, styrene isoprene styrene block copolymer (SIS) etc.；
Siliceous soft polymer: dimethyl polysiloxane, diphenylpolysiloxane, polysiloxanediol Deng；
Olefines soft polymer: liquid polyethylene, polypropylene, poly-1-butylene, ethene-alpha-olefin copolymerization Thing, propylene-alpha-olefin copolymers, ethylene-propylene-diene copolymer (EPDM), ethylene-propylene, Styrene Copolymer etc.；
Vinyl-based soft polymer: polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, second Vinyl acetate-styrol copolymer etc.；
Epoxies soft polymer: poly(ethylene oxide), poly(propylene oxide), epichlorohydrin rubber etc.；
Fluorine-containing soft polymer: vinylidene class rubber, tetrafluoroethylene-acrylic rubber etc.；
Other soft polymer: natural rubber, polypeptide, protein, polyester-type thermoplastic elastomer, Polyvinyl chloride-base thermoplastic elastomer, polyamide-type thermoplastic elastomer etc.；Etc..These soft polymers Can have cross-linked structure, alternatively, it is also possible to import functional group by modification.
The amount of the binding agent for electrode in electrode active material layer is preferably with respect to electrode active material 100 matter Amount part is 0.1～5 mass parts, more preferably 0.2～4 mass parts, particularly preferably 0.5～3 mass parts.Logical Crossing and making the binding agent for electrode amount in electrode active material layer is above-mentioned scope, can not hinder cell reaction Ground inhibitory activity material departs from from electrode.
In order to make electrode, prepare binding agent for electrode with the form of solution or dispersion liquid.Viscosity now Usually 1～300, the scope of 000mPa s, preferably 50～10,000mPa s.Above-mentioned viscosity is for using B Type viscometer 25 DEG C, measure under conditions of rotating speed 60rpm time value.
(arbitrary additive)
In the present invention, electrode active material layer bonds except above-mentioned electrode active material and electrode Beyond agent, it is also possible to containing the arbitrary additive such as conductive imparting material, reinforcing material.As conduction Give material, can enumerate；Acetylene black, Ketjen black, white carbon black, graphite, gas-phase growth of carbon fibre, carbon The conductive carbon such as nanotube.Can enumerate: the carbon dusts such as graphite, the fiber of various metal and paper tinsel etc..Make For reinforcing material, it is possible to use various inorganic and the most spherical, tabular, bar-shaped or fibrous filler. By using electric conductivity to give material, electrode active material electrical contact each other can be improved, for lithium In the case of ion secondary battery, discharge-rate characteristic can be improved.Relative to electrode active material 100 Mass parts, electric conductivity gives the usage amount of material and reinforcing material and is usually 0～20 mass parts, is preferably 1～10 mass parts.It addition, isothiazoline based compound and chela can also be contained in electrode active material layer Polymerisable compounds
Electrode active material layer can make the slurry containing electrode active material, binding agent for electrode and solvent (hereinafter also referred to as " electrode slurry ") is attached on collector body be formed.
As solvent, as long as lysis electrodes binding agent or binding agent for electrode is dispersed into granular Solvent, the preferably solvent of lysis electrodes binding agent.If using the solvent of lysis electrodes binding agent, Then binding agent for electrode can be adsorbed in electrode active material and the surface of arbitrary additive, thus can make electricity The decentralized stabilization of pole active substance etc..
As the solvent for electrode slurry, it is possible to use any solvent in water and organic solvent.Make For organic solvent, can enumerate: the annular aliphatic hydro carbons such as Pentamethylene., hexamethylene；Toluene, dimethylbenzene Etc. aromatic hydrocarbon；The ketone such as butanone, Ketohexamethylene；Ethyl acetate, butyl acetate, gamma-butyrolacton, ε- The esters such as caprolactone；The nitrile such as acetonitrile, propionitrile；The ethers such as oxolane, ethylene glycol diethyl ether；Methanol, The alcohols such as ethanol, isopropanol, ethylene glycol, glycol monoethyl ether；N-Methyl pyrrolidone, N, N-diformazan The amide-types such as base Methanamide.Can suitably select to use in the case of considering in terms of rate of drying and environment In these solvents a kind or be mixed with two or more.
Electrode slurry can contain viscosifier etc. further and show the additive of various function.As Viscosifier, can use the polymer dissolving in solvent for electrode slurry.Specifically, can make With the viscosifier illustrated in the perforated membrane slurry of the present invention.The usage amount of viscosifier is preferably with respect to electrode active Property material 100 mass parts is 0.5～1.5 mass parts.If the usage amount of viscosifier is above-mentioned scope, then electrode With the screening characteristics of slurry and good with the adaptation of collector body.
And then, in electrode slurry, in addition to mentioned component, in order to improve stability and the longevity of battery Life, it is also possible to use trifluoro propylene carbonate, vinylene carbonate, catechol carbonate, 1,6-dioxa Spiral shell [4,4] nonane-2,7-diketone, 12-crown-4-ether etc..It addition, these compositions can also be containing at electricity described later Solve in liquid and use.
According to the kind of electrode active material and binding agent for electrode etc., adjust the solvent in electrode slurry Amount, reach be suitable to coating viscosity and use.Specifically, preferably it is adjusted, makes Electrode active material, binding agent for electrode and electric conductivity in electrode slurry gives material etc. and adds arbitrarily The concentration of the total solid constituent adding agent reaches 30～90 mass %, more preferably 40～80 mass % and uses.
Mixer is used electrode active material, binding agent for electrode, the electric conductivity that is added as needed on to be composed Give the arbitrary additives such as material and solvent mixes, thus obtain electrode slurry.Mixing can also Above-mentioned each composition is supplied in mixer in the lump mix.Use using electrode active material, electrode In the case of binding agent, electric conductivity imparting material and viscosifier are as the constituent of electrode slurry, will Electric conductivity gives material and viscosifier mix in a solvent and makes electric conductivity give material is separated into microgranular, Then add binding agent for electrode, electrode active material, mix the most again, thus can make slurry Dispersibility improves, therefore preferably.As mixer, it is possible to use ball mill, sand mill, pigment dispersion machine, Meat mill, ultrasonic dispersing machine, homogenizer, planetary stirring machine, Hobart's blender etc., if using Ball mill, then can suppress electric conductivity to give material, the cohesion of electrode active material, therefore preferably.
The granularity of electrode slurry is preferably below 35 μm, more preferably below 25 μm.If slurry Granularity be above-mentioned scope, then can get the electrode of homogenizing.
(collector body)
As long as collector body is to have electric conductivity and have the material of electrochemistry durability and be just not particularly limited, From the viewpoint of there is thermostability, the most such as ferrum, copper, aluminum, nickel, rustless steel, titanium, tantalum, gold, The metal materials such as platinum.Wherein, as the positive pole use of lithium rechargeable battery, particularly preferred aluminum, as lithium The negative pole use of ion secondary battery, particularly preferred copper.The shape of collector body is not particularly limited, preferably thick The lamellar collector body of degree 0.001～about 0.5mm.For collector body, in order to improve electrode active material layer Adhesion strength, after being roughened the most in advance use.As roughening method, can enumerate: Mechanical polishing method, electrobrightening method, chemical polishing etc..In mechanical polishing method, can use and be adhered with The sand paper of polishing agent granule, grinding stone, corundum (emery buff), possesses the line brush etc. of steel wire etc..It addition, In order to improve adhesion strength and the electric conductivity of electrode active material layer, it is also possible in collector body surface is formed Interbed.
As long as the manufacture method of electrode active material layer is at least one side of above-mentioned collector body, preferred two sides Make the method that electrode active material layer is bonded as stratiform.Such as, above-mentioned electrode slurry is coated on On collector body and be dried, then 120 DEG C of heat treated of more than 1 hour carried out above, form electricity Pole active material layer.The method of coating electrode slurry is not particularly limited on the current collector.The most permissible Enumerate: scraper for coating method, infusion process, inverse roller method, direct rolling method, intagliotype, squeezing and pressing method, brushing The methods such as method.As drying means, can enumerate: utilize such as warm air, hot blast, low wet wind be dried, The seasoning that vacuum drying, utilization (far) infrared ray or electron beam etc. irradiate.
Then, moulding press or roll squeezer are preferably used, reduce electrode active material layer by pressurized treatments Voidage.The preferred scope of voidage is 5～15%, more preferably 7～13%.If voidage is too high, Then charge efficiency and discharging efficiency are deteriorated.In the case of voidage is too low, can produce and be difficult to obtain high body Long-pending capacity or electrode active material layer easily peel off and easily produce bad such problem.Additionally, In the case of using curable polymer, preferably solidify.
For the thickness of electrode active material layer, positive pole, negative pole are all usually 5～300 μm, are preferably 10～250 μm.
The electrode for secondary battery of the present invention by being bonded as the electricity of the collector body of stratiform at electrode active material layer The secondary cell perforated membrane of active material layer surface, the pole superimposed layer present invention manufactures.
Laminating method is not particularly limited, and can enumerate: explanation in the manufacture method of above-mentioned perforated membrane ～the method for (III) (I).
(4) secondary battery separator
The secondary battery separator of the present invention comprises the above-mentioned secondary of institute's lamination on organic dividing plate, this organic dividing plate Battery perforated membrane forms.That is, the secondary battery separator of the present invention is by the surface superimposed layer at organic dividing plate Above-mentioned secondary cell perforated membrane forms.
(organic dividing plate)
As the organic dividing plate of lithium rechargeable battery, can use the vistanex such as polyethylene, polypropylene, Comprise the known dividing plate such as dividing plate of aromatic polyamide resin.
As the organic dividing plate for the present invention, can use and not there is electronic conductivity and there is ionic conduction Property, the multiple aperture plasma membrane that patience is high and aperture is fine of organic solvent, can enumerate by such as TPO (poly- Ethylene, polypropylene, polybutene, polrvinyl chloride) and the resin formation such as their mixture or copolymer micro- Perforated membrane, by polyethylene terephthalate, polycyclic alkene, polyether sulfone, polyamide, polyimides, The resin formation such as polyimide amide, Nomex, polycyclic alkene, nylon, politef micro-many Pore membrane or by polyolefin fibrids braiding collector body or its non-woven fabrics, insulating properties material grains Aggregation etc..Wherein, excellent from the screening characteristics of the perforated membrane slurry of the present invention, can be whole with thinning dividing plate The thickness of body, the active substance ratio improved in battery thus from the standpoint of improving the capacity of unit volume, The micro-porous film preferably formed by polyolefin resin.
The thickness of organic dividing plate is usually 0.5～40 μm, preferably 1～30 μm, more preferably 1～20 μm.If this scope, then the resistance that the organic dividing plate in battery brings diminishes.It addition, by this Bright perforated membrane slurry coating operability when organic dividing plate is good.
In the present invention, as the polyolefin resin of the material as organic dividing plate, can enumerate: poly- The homopolymer of ethylene, polypropylene etc., copolymer and their mixture.As polyethylene, permissible Enumerate low-density, Midst density, highdensity polyethylene, from the viewpoint of puncture strength and mechanical strength, The most highdensity polyethylene.It addition, consider from the purpose giving flexibility, it is also possible to by above-mentioned poly-second Two or more mixing in alkene.For the polymerization catalyst of these polyethylene it is not also specifically limited, permissible Enumerate: Z-N series catalysts, Philips series catalysts and metallocene series catalysts etc..From holding concurrently From the viewpoint of standby mechanical strength and high-permeability, the viscosity-average molecular weight of polyethylene is preferably 100,000～1200 Ten thousand, more preferably 200,000～3,000,000.As polypropylene, can enumerate: homopolymer, random copolymer, Block copolymer, can mix one or two or more kinds and use.It addition, polymerization catalyst does not has yet Limit especially, can enumerate: Z-N series catalysts and metallocene series catalysts etc..It addition, it is vertical Body regularity it is not also specifically limited, isotaxy, syndiotaxy and atactic can be used, and from From the standpoint of Lian Jia, isotactic polypropylene is preferably used.And then, it is also possible to do not damaging the present invention Effect in the range of in polyolefin the appropriate polyolefin added beyond polyethylene or polypropylene and antioxygen The additive such as agent, nucleator.
Method as the organic dividing plate making TPO, it is possible to use public method, such as Can select from following method: after polypropylene, polyethylene are melt extruded and be filmed, at low temperature Under make it anneal, make crystallized domains grow, stretch in this condition, make non-crystalline areas stretch, thus Form the dry method of micro-porous film；By hydrocarbon solvent and other low molecule material and polypropylene, polyethylene After mixing so that it is film forming, then, collect for solvent in amorphous phase and low molecule and initially form island The film of phase, by using other readily volatilized solvent to remove this solvent, low molecule, is consequently formed micro- The wet method etc. of perforated membrane.Wherein, for dropping low-resistance purpose, being readily obtained the side in big space Face considers, preferred dry method.
For controlling intensity and hardness, the purpose of percent thermal shrinkage, the organic dividing plate for the present invention can also Containing arbitrary filler and compound.It addition, in the case of the perforated membrane of the lamination present invention, go out Improve in the adaptation making organic dividing plate and perforated membrane or reduce and make relative to the surface tension of electrolyte The purpose that the impregnation of liquid improves, it is also possible to carry out with low molecular compound or macromolecular compound in advance Cladding processes or carries out at the plasmas such as electromagnetic wire process, corona discharge-plasma gas such as ultraviolet Reason.Particularly high from the impregnation of electrolyte, be readily available adaptation with above-mentioned perforated membrane in terms of examine Consider, be preferably coated with the macromolecular compound containing carboxylic acid group, hydroxyl and sulfonic group isopolarity group Process.
The secondary battery separator of the present invention is by the secondary cell in above-mentioned organic dividing plate superimposed layer present invention Perforated membrane manufactures.
Laminating method is not particularly limited, and can enumerate explanation in the manufacture method of above-mentioned perforated membrane ～the method for (III) (I).
(5) secondary cell
The secondary cell of the present invention contains positive pole, negative pole, organic dividing plate and electrolyte, at positive pole, negative pole And any materials superimposed layer of organic dividing plate has above-mentioned secondary cell perforated membrane.
(electrolyte)
As electrolyte, use the organic electrolyte dissolving supporting electrolyte in organic solvent.Make For supporting electrolyte, lithium salts can be used.As lithium salts, it is not particularly limited, can enumerate: LiPF6、 LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、 (CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2) NLi etc..Wherein, be preferably easily soluble in solvent and Show the LiPF of high degree of dissociation6、LiClO4、CF3SO3Li.These can also be applied in combination more than two kinds. Owing to more using the supporting electrolyte then lithium ion conductivity that degree of dissociation is high the highest, therefore, it can according to propping up Hold the kind regulation lithium ion conductivity of electrolyte.
As the organic solvent for electrolyte, as long as the solvent that can dissolve supporting electrolyte does not just have It is particularly limited to, preferably uses dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), the carbonates such as propylene carbonate (PC), butylene carbonate (BC), Ethyl methyl carbonate (MEC)； The esters such as gamma-butyrolacton, methyl formate；The ethers such as 1,2-dimethoxy-ethane, oxolane；Sulfolane, The sulfur-containing compound classes such as dimethyl sulfoxide.Alternatively, it is also possible to use the mixed liquor of these solvents.Wherein, by In the voltage belt field width that carbonates dielectric constant is high, stable, therefore preferably.Viscous due to the solvent that uses Spending the lowest, lithium ion conductivity becomes the highest, therefore, can regulate lithium ion conduction according to the kind of solvent Rate.
As the concrete manufacture method of secondary cell, can enumerate: by positive pole and negative pole across organic every Plate overlaps, and crimped according to cell shapes, bending etc. puts into battery case, to battery case Middle injection electrolyte the method sealed.The perforated membrane of the present invention be stacked in positive pole, negative pole and organic every Plate any on.The perforated membrane of the present invention is stacked on positive pole, negative pole, organic dividing plate method the most above-mentioned (I) or (II) method described in.It addition, described in the method for (III) described above, it is also possible to the most independently will Perforated membrane is stacked on positive pole, negative pole or organic dividing plate.Expansion alloy, insurance can also be put into as required The overcurrent such as silk, PTC-element prevent element, lead plate etc. from preventing the pressure of inside battery from rising, mistake Discharge and recharge.The shape of battery can be Coin shape, coin shape, flap-type, cylinder type, square, platypelloid type Arbitrary shape in Deng.
In the secondary cell of the present invention, preferably the perforated membrane of the present invention is stacked on the electricity of negative or positive electrode Active material layer surface, pole.By the perforated membrane of the present invention being stacked on electrode active material layer surface, i.e. Make organic dividing plate shrink because being heated, the short circuit between positive pole/negative pole also will not occur, high security can be kept. It addition, by the perforated membrane of the present invention is stacked on electrode active material layer surface, though do not have organic every Plate, perforated membrane can also play the function as dividing plate, it is possible to low-cost production's secondary cell.It addition, In the case of using organic dividing plate, also will not fill the hole being formed in baffle surface, can show Higher multiplying power property.
Embodiment
Hereinafter, the present invention will be described to enumerate embodiment, but the present invention is not limited to this.Need Bright, part in the present embodiment and % unless otherwise specified, are then quality criteria.In embodiment And in comparative example, various physical property are carried out as follows evaluation.
<heat resisting temperature (T10 value) of non-conductive organic granular>
Under nitrogen atmosphere, utilize thermobalance to heat with programming rate 10 DEG C/min from 30 DEG C, obtain non- The loss of weight ratio of conductive particle reaches the temperature [DEG C] of 10 mass %, as heat resisting temperature.
< electrode for secondary battery (electrode of band perforated membrane) or secondary battery separator (organic dividing plate of band perforated membrane) Flexibility and powder falling >
By electrode for secondary battery (electrode of band perforated membrane) or secondary battery separator (organic dividing plate of band perforated membrane) It is cut into the rectangle of width 1cm × length 5cm, makes test film.Make the contrary with perforated membrane side of test film Be placed on face-down on desk, at central authorities (position of end 2.5cm) and the perforated membrane of length direction The stainless steel bar of diameter 1mm is set with couching in the width direction on the face that side is contrary.With this stainless steel bar it is Test film is bent 180 degree and makes outside porous membrane layer is by center.10 test films are tested, Sweep observation to the porous membrane layer of each test film has flawless or powder falling, and is entered by following benchmark Row judges.Crackle, peeling powder falling are the fewest, represent on electrode active material layer or formation on organic dividing plate Flexibility and the powder falling of perforated membrane are the most excellent.
A: all do not find crackle and powder falling in whole 10.
B: find crackle or powder falling in 1～3 in 10.
C: find crackle or powder falling in 4～6 in 10.
D: find crackle or powder falling in 7～9 in 10.
E: the whole middle discovery crackle in 10 or powder falling.
<water quantities of secondary cell perforated membrane>
By electrode for secondary battery (electrode of band perforated membrane) or secondary battery separator (organic dividing plate of band perforated membrane) It is cut into width 10cm × length 10cm, makes test film.By test film at temperature 25 DEG C, dew point-60 DEG C 24 hours arranged below.Then, use coulometric titration formula moisture meter by karr-Fei Xiefa The water quantities of (JISK-0068 (2001) moisture vaporization method, gasification temperature 150 DEG C) determination test sheet, calculates many The water quantities of the per unit volume of pore membrane.The water quantities of the per unit volume of perforated membrane is the fewest, more will not be by Moisture causes the side reaction in battery, and battery behavior will not be occurred to reduce, therefore preferably.
A: less than 1.0mg/cm3
B:1.0mg/cm3Less than 1.5mg/cm3
C:1.5mg/cm3Less than 3.0mg/cm3
D:3.0mg/cm3Above
<metals content impurity>
Use inductively coupled plasma emission spectrophotometer (ICP-AES；SII Nanotechnology Company) to the metal impurities (Ca, Co, Cr, Cu, Fe, Mg, Ni, Zn) in non-conductive organic granular Total content (ppm) carried out quantitative analysis.The content of the metal impurities in non-conductive organic granular is more Few, battery behavior more will not be occurred to reduce, therefore preferably.
A: less than 50ppm
B:50ppm is less than 100ppm
C:100ppm is less than 200ppm
More than D:200ppm
<cycle characteristics of secondary cell>
About the Coin-shaped battery of Unit 10, the temperature chamber of 60 DEG C repeats the perseverance by 0.2C Determine current method charge to 4.3V and be discharged to the discharge and recharge of 3.0V, measure discharge capacity.By Unit 10 Meansigma methods, as measured value, calculates discharge capacity the putting relative to the 5th circulation of the 60th circulation with percentage rate The ratio of capacitance, obtains capability retention, with following benchmark evaluation cycle characteristics.This value is the highest, follows Ring property is the most excellent.
More than A:90%
B:80% is less than 90%
C:70% is less than 80%
D:60% is less than 70%
E: less than 60%
(embodiment 1)
<manufacture of (1) seeding polymerization composition granule A>
The reactor possess blender is put into styrene 100 parts, dodecylbenzene sodium sulfonate 1.0 parts, Ion exchange water 100 parts and potassium peroxydisulfate 0.5 part, be polymerized 8 hours at 80 DEG C.Thus, obtain The aqueous dispersion of the seeding polymerization composition granule A of mean diameter 60nm.
<manufacture of (2) seeding polymerization composition granule B>
The moisture of the seeding polymerization composition granule A obtained in operation (1) is put in the reactor possess blender A prose style free from parallelism 2 parts (in terms of solid constituent benchmark, i.e. with the weight basis of seeding polymerization composition granule A), ten 0.2 part of dialkyl benzene sulfonic acids sodium, potassium peroxydisulfate 0.5 part and ion exchange water 100 parts, mix, Obtain mixture, be warming up to 80 DEG C.On the other hand, benzene mixed ethylene 97 parts, methyl in another container 3 parts of acrylic acid, tertiary lauryl mercaptan 4 parts, dodecylbenzene sodium sulfonate 0.5 part and ion exchange water 100 parts, it is prepared for the dispersion of monomer mixture.By the dispersion of this monomer mixture through 4 hours continuously Ground adds in said mixture so that it is polymerization.During adding the dispersion of monomer mixture continuously, The temperature of reaction system is maintained 80 DEG C, is reacted.Add after terminating continuously, further at 90 DEG C Lower continuation reacts 3 hours.
Thus obtain the aqueous dispersion of the seeding polymerization composition granule B of mean diameter 200nm.
<manufacture of (3) non-conductive organic granular>
Then, in the reactor possess blender, put into the seeding polymerization composition granule B obtained in operation (2) Aqueous dispersion 10 parts (in terms of solid constituent benchmark, i.e. with the weight basis of seeding polymerization composition granule B Meter), monomer mixture (divinylbenzene and the mixture of vinyl xylene, ethyl vinyl benzene, monomer mixing ratio: divinyl Base benzene/vinyl xylene, ethyl vinyl benzene=60/40, chemical company of Nippon Steel system, goods name: DVB-570) 88.5 parts, 2-acrylamide-2-methyl propane sulfonic 1.5 parts, dodecylbenzene sodium sulfonate 1.0 parts, as polymerization initiator Peroxide-2-ethyl hexanoic acid tert-butyl (You company system, trade name: Perbutyl O) 5 parts and ion Exchanged water 200 parts, stirs 12 hours at 35 DEG C, thus makes seeding polymerization composition granule B fully absorb Monomer mixture and polymerization initiator.Then, it is polymerized 4 hours at 90 DEG C.Then, steaming is imported Gas removes unreacted monomer.
Thus, the aqueous dispersion of the non-conductive organic granular of mean diameter 0.4 μm is obtained.
Formed from seed polymer granule and start to obtaining the monomer that used non-conductive organic granular (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and 2-acrylamide-2-methyl-prop sulphur Acid) composition and the heat resisting temperature (T10 value) of non-conductive organic granular, binding agent can be with heat The content of functional group's (sulfonic group) that crosslinkable groups (epoxy radicals) cross-links and metals content impurity such as table 1 Shown in.
<manufacture of (4) binding agent>
Ion exchange water 70 parts, dodecylbenzene sodium sulfonate 0.4 is put in the reactor possess blender Part and potassium peroxydisulfate 0.3 part, carry out being obtained by mixing mixture, be warming up to 60 DEG C.
On the other hand, hybrid ionic exchanged water 50 parts, dodecylbenzene sodium sulfonate 0.8 in another container Part, 2-EHA 77.7 parts, acrylonitrile 20 parts, glycidyl methacrylate 2.3 parts, Obtain monomer mixture.
This monomer mixture was added continuously in said mixture through 4 hours so that it is polymerization.Continuously In adding procedure, the temperature of reaction system is maintained 60 DEG C, is reacted.Add continuously after terminating, enter One step continues reaction 3 hours at 70 DEG C, and (binding agent is water-dispersible to obtain the aqueous dispersions containing binding agent Liquid).
After the binding agent aqueous dispersions obtained is cooled to 25 DEG C, being added to ammonia by pH regulator is 7, Then, import steam and remove unreacted monomer.Then, relative to the solid constituent 100 parts of binding agent, Add ethylenediaminetetraacetic acid 0.25 part immediately, they are mixed, carries out further with ion exchange water The adjustment of solid component concentration, is carried out with the stainless steel metal gauze of 200 mesh (mesh about 77 μm) Filter, obtain perforated membrane binding agent water-dispersible of mean diameter 100nm, solid component concentration 40% Liquid.
(Glycidyl methacrylate is sweet to have the vinyl monomer of heat cross-linking group in perforated membrane binding agent Grease) polymerized unit containing ratio be 2.3%, the containing of the polymerized unit of (methyl) acrylate monomer Ratio is 77.7%, the polymerized unit of 'alpha ', ' bela '-unsaturated nitrile monomer be 20% containing ratio.
<manufacture of (5) perforated membrane slurry>
Use degree of etherification falling be 0.8～1.0,1% solution viscosity be the carboxymethyl cellulose of 10～20mPa s (Daicel chemical industry Co., Ltd. Daicel1220) is prepared for 1% aqueous solution as viscosifier.
The porous that will obtain in the aqueous dispersion of non-conductive organic granular obtained in operation (3), operation (4) The aqueous dispersions of film binding agent and 1% aqueous solution of carboxymethyl cellulose with solids by weight ratio are The mode of 83.1:12.3:4.6 mixes in water, adds the water as solvent further, uses ball mill Make it disperse, obtain perforated membrane slurry.Wherein, the raw material (solid constituent beyond water in perforated membrane slurry is made Total) content be 50 mass %.
<manufacture of (6) positive pole>
Add in as the LiMn2O4 with spinel structure 95 parts of positive active material and use as electrode The PVDF (Kynoar, Wu Yu chemical company system, trade name: KF-1100) of binding agent also makes PVDF It is calculated as 3 parts with solid constituent conversion amount, is subsequently adding acetylene black 2 parts and N-Methyl pyrrolidone 20 Part, they are mixed with planetary stirring machine, obtains positive pole electrod composition (the positive pole slurry of pulp-like Material).This positive pole slurry is coated the one side of the aluminium foil of thickness 18 μm, at 120 DEG C, is dried 3 little Shi Hou, carries out roll-in and prepares the positive pole with positive electrode active material layer that gross thickness is 100 μm.
<manufacture of (7) negative pole>
Using as particle diameter 20 μm of negative electrode active material, specific surface area 4.2m298 parts of the graphite of/g, conduct The solid of the SBR (SBR styrene butadiene rubbers, glass transition temperature :-10 DEG C) of binding agent for electrode becomes Divide conversion amount 1 part mixing, the most further mixing carboxy methyl cellulose 1.0 parts, further Add the water as solvent, they are mixed with planetary stirring machine, the negative pole electrode of preparation pulp-like Compositions (negative pole slurry).This negative pole slurry is coated the one side of the Copper Foil of thickness 18 μm, 110 Be dried after 3 hours at DEG C, carry out roll-in system, obtain gross thickness be 60 μm there is negative electrode active material The negative pole of layer.
<manufacture of (8) secondary battery separator (organic dividing plate of band perforated membrane)>
The polypropylene dividing plate (porosity 55%, thickness 25 μm) being ready to pass through the monolayer that dry process manufactures is made For organic dividing plate.Using bar is 5 μm with dried thickness on a side surface of this organic dividing plate The perforated membrane slurry obtained in mode painting process (5), obtains pulp layer, is dried by pulp layer at 50 DEG C 10 minutes, form perforated membrane.It follows that form porous similarly on the opposite side surface of organic dividing plate Film, obtains organic dividing plate on two sides with the band perforated membrane of perforated membrane.
The manufacture of secondary cell of secondary battery separator (organic dividing plate of band perforated membrane)<(9) have>
The positive pole obtained in operation (6) is cut into the circle of diameter 13mm, obtains the positive pole of circle.By work The negative pole obtained in sequence (7) is cut into the circle of diameter 14mm, obtains the negative pole of circle.It addition, by operation (8) organic dividing plate of the band perforated membrane obtained in is cut into the circle of diameter 18mm, obtains the band porous of circle Organic dividing plate of film.
Mounting circle on the inner bottom surface of the Coin shape exterior package container of the stainless steel being provided with polypropylene liner The positive pole of shape, loads organic dividing plate of the band perforated membrane of circle thereon, loads circle the most thereon Negative pole, they are accommodated in container.Circular positive pole faces out packaging container with the face of its aluminium foil side Bottom surface side, the face of positive electrode active material layer side load towards the mode of upside.Circular negative pole is born with it The face of active material layer side, pole towards circular organic bulkhead sides of band perforated membrane, Copper Foil side face towards The mode of upside loads.By being vacuum dried 24 hours at 105 DEG C by this container, make binding agent and non- The crosslinking of electric conductivity organic fine particles is carried out, and is then removed by the residual moisture in system.
Electrolyte is injected in a reservoir, via the dressing outside of polypropylene liner in the way of not residual air Cover the stainless lid of thickness 0.2mm on device and fix, by battery can seal, manufactured diameter 20mm, The lithium rechargeable battery (coin battery CR2032) of thickness about 3.2mm.As electrolyte, employ Ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed with EC:DEC=1:2 (volumetric ratios at 20 DEG C) Mixed solvent in dissolve LiPF with the concentration of 1 mol/L6Solution.
<(10) are evaluated>
To the flexibility of organic dividing plate, powder falling and the water quantities of the band perforated membrane obtained and obtain The cycle characteristics of secondary cell is evaluated.Result is as shown in table 1.
(embodiment 2)
The non-conductive organic granular obtained in the operation (1) of replacement embodiment 1～(3), employs following Non-conductive organic granular.It addition, replace the perforated membrane binding agent obtained in the operation (4) of embodiment 1, Employ following perforated membrane binding agent.This non-conductive organic granular and this perforated membrane is used to bond Agent manufactures perforated membrane slurry, in addition, carries out operation similarly to Example 1, has obtained band porous Organic dividing plate of film and secondary cell are also evaluated.Result is as shown in table 1.
<manufacture of non-conductive organic granular>
The moisture of the seeding polymerization composition granule B obtained in operation (2) is put in the reactor possess blender A prose style free from parallelism 10 parts (in terms of solid constituent benchmark, i.e. with the weight basis of seeding polymerization composition granule B), list Body mixture (divinylbenzene and the mixture of 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, 2-third Acrylamide-2-methyl propane sulfonic acid 0.4 part, dodecylbenzene sodium sulfonate 1.0 parts, mistake as polymerization initiator Oxidation-2 ethyl hexanoic acid the tert-butyl ester (You company system, trade name: Perbutyl O) 5 parts and ion exchange 200 parts of water, stirs 12 hours at 35 DEG C, thus makes seeding polymerization composition granule B fully absorb monomer Mixture and polymerization initiator.Then, it is polymerized 4 hours at 90 DEG C.Then, import steam to remove Remove unreacted monomer.
Thus, the aqueous dispersion of the non-conductive organic granular of mean diameter 0.4 μm is obtained.
Formed from seed polymer granule and start to obtaining the monomer that used non-conductive organic granular (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and 2-acrylamide-2-methyl-prop sulphur Acid) composition and the heat resisting temperature (T10 value) of non-conductive organic granular, binding agent can be with heat The content of functional group's (sulfonic group) that crosslinkable groups (epoxy radicals) cross-links and metals content impurity such as table 1 institute Show.
<manufacture of binding agent>
Ion exchange water 70 parts, dodecylbenzene sodium sulfonate 0.4 is put in the reactor possess blender Part and potassium peroxydisulfate 0.3 part, carry out being obtained by mixing mixture, be warming up to 60 DEG C.
On the other hand, hybrid ionic exchanged water 50 parts, dodecylbenzene sodium sulfonate 0.8 in another container Part, 2-EHA 78.4 parts, acrylonitrile 21 parts, glycidyl methacrylate 0.6 part, Obtain monomer mixture.
This monomer mixture was added continuously in said mixture through 4 hours so that it is polymerization.Continuously In adding procedure, the temperature of reaction system is maintained 60 DEG C, is reacted.Add continuously after terminating, enter One step continues reaction 3 hours at 70 DEG C, and (binding agent is water-dispersible to obtain the aqueous dispersions containing binding agent Liquid).
After the binding agent aqueous dispersions obtained is cooled to 25 DEG C, being added to ammonia by pH regulator is 7, It is then introduced into steam and removes unreacted monomer.Then, relative to the solid constituent 100 parts of binding agent, Add ethylenediaminetetraacetic acid 0.25 part immediately, they are mixed, carries out further with ion exchange water The adjustment of solid component concentration, is carried out with the stainless steel metal gauze of 200 mesh (mesh about 77 μm) Filter, obtain perforated membrane binding agent water-dispersible of mean diameter 100nm, solid component concentration 40% Liquid.
Vinyl monomer (the Glycidyl methacrylate with heat cross-linking group in perforated membrane binding agent Glyceride) polymerized unit containing ratio be 0.6%, the containing of the polymerized unit of (methyl) acrylate monomer To have ratio be 78.4%, the polymerized unit of 'alpha ', ' bela '-unsaturated nitrile monomer be 21% containing ratio.
(embodiment 3)
The non-conductive organic granular obtained in the operation (1) of replacement embodiment 1～(3), employs following Non-conductive organic granular.It addition, replace the perforated membrane binding agent obtained in the operation (4) of embodiment 1, Employ following perforated membrane binding agent.This non-conductive organic granular and this perforated membrane is used to bond Agent manufactures perforated membrane slurry, in addition, carries out operation similarly to Example 1, has obtained band porous Organic dividing plate of film and secondary cell are also evaluated.Result is as shown in table 1.
<manufacture of non-conductive organic granular>
The moisture of the seeding polymerization composition granule B obtained in operation (2) is put in the reactor possess blender A prose style free from parallelism 10 parts (in terms of solid constituent benchmark, i.e. with the weight basis of seeding polymerization composition granule B), list Body mixture (divinylbenzene and the mixture of 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-third Acrylamide-2-methyl propane sulfonic acid 2.8 parts, dodecylbenzene sodium sulfonate 1.0 parts, mistake as polymerization initiator Oxidation-2 ethyl hexanoic acid the tert-butyl ester (You company system, trade name: Perbutyl O) 5 parts and ion exchange 200 parts of water, stirs 12 hours at 35 DEG C, thus makes seeding polymerization composition granule B fully absorb monomer Mixture and polymerization initiator.Then, it is polymerized 4 hours at 90 DEG C.Then, import steam to remove Remove unreacted monomer.
Thus, the aqueous dispersion of the non-conductive organic granular of mean diameter 0.4 μm is obtained.
Formed from seed polymer granule and start to obtaining the monomer that used non-conductive organic granular (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and 2-acrylamide-2-methyl-prop sulphur Acid) composition and the heat resisting temperature (T10 value) of non-conductive organic granular, binding agent can be with heat The content of functional group's (sulfonic group) that crosslinkable groups (epoxy radicals) cross-links and metals content impurity such as table 1 institute Show.
<manufacture of binding agent>
Ion exchange water 70 parts, dodecylbenzene sodium sulfonate 0.4 is put in the reactor possess blender Part and potassium peroxydisulfate 0.3 part, carry out being obtained by mixing mixture, be warming up to 60 DEG C.
On the other hand, hybrid ionic exchanged water 50 parts, dodecylbenzene sodium sulfonate 0.8 in another container Part, 2-EHA 76.5 parts, acrylonitrile 19 parts, glycidyl methacrylate 4.5 parts, Obtain monomer mixture.
This monomer mixture was added continuously in said mixture through 4 hours so that it is polymerization.Continuously In adding procedure, the temperature of reaction system is maintained 60 DEG C, is reacted.Add continuously after terminating, enter One step continues reaction 3 hours at 70 DEG C, and (binding agent is water-dispersible to obtain the aqueous dispersions containing binding agent Liquid).
After the binding agent aqueous dispersions obtained is cooled to 25 DEG C, being added to ammonia by pH regulator is 7, It is then introduced into steam and removes unreacted monomer.Then, relative to the solid constituent 100 parts of binding agent, Add ethylenediaminetetraacetic acid 0.25 part immediately, they are mixed, carries out further with ion exchange water The adjustment of solid component concentration, is carried out with the stainless steel metal gauze of 200 mesh (mesh about 77 μm) Filter, obtain perforated membrane binding agent water-dispersible of mean diameter 100nm, solid component concentration 40% Liquid.
Vinyl monomer (the Glycidyl methacrylate with heat cross-linking group in perforated membrane binding agent Glyceride) polymerized unit containing ratio be 4.5%, the containing of the polymerized unit of (methyl) acrylate monomer To have ratio be 76.5%, the polymerized unit of 'alpha ', ' bela '-unsaturated nitrile monomer be 19% containing ratio.
(embodiment 4)
Replace the perforated membrane binding agent obtained in the operation (4) of embodiment 1, use following perforated membrane to use Binding agent has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, obtains Organic dividing plate with perforated membrane and secondary cell are also evaluated.Result is as shown in table 1.
<manufacture of binding agent>
Ion exchange water 70 parts, dodecylbenzene sodium sulfonate 0.4 is put in the reactor possess blender Part and potassium peroxydisulfate 0.3 part, carry out being obtained by mixing mixture, be warming up to 60 DEG C.
On the other hand, hybrid ionic exchanged water 50 parts, dodecylbenzene sodium sulfonate 0.8 in another container Part, 2-EHA 91 parts, acrylonitrile 7 parts, glycidyl methacrylate 2 parts, To monomer mixture.
This monomer mixture was added continuously in said mixture through 4 hours so that it is polymerization.Continuously In adding procedure, the temperature of reaction system is maintained 60 DEG C, is reacted.Add continuously after terminating, enter One step continues reaction 3 hours at 70 DEG C, and (binding agent is water-dispersible to obtain the aqueous dispersions containing binding agent Liquid).
After the binding agent aqueous dispersions obtained is cooled to 25 DEG C, being added to ammonia by pH regulator is 7, It is then introduced into steam and removes unreacted monomer.Then, relative to the solid constituent 100 parts of binding agent, Add ethylenediaminetetraacetic acid 0.25 part immediately, they are mixed, carries out further with ion exchange water The adjustment of solid component concentration, is carried out with the stainless steel metal gauze of 200 mesh (mesh about 77 μm) Filter, obtain perforated membrane binding agent water-dispersible of mean diameter 100nm, solid component concentration 40% Liquid.
Vinyl monomer (the Glycidyl methacrylate with heat cross-linking group in perforated membrane binding agent Glyceride) polymerized unit containing ratio be 2%, the containing of the polymerized unit of (methyl) acrylate monomer Ratio is 91%, the polymerized unit of 'alpha ', ' bela '-unsaturated nitrile monomer be 7% containing ratio.
(embodiment 5)
Replace the perforated membrane binding agent obtained in the operation (4) of embodiment 1, use following perforated membrane to use Binding agent has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, obtains Organic dividing plate with perforated membrane and secondary cell are also evaluated.Result is as shown in table 1.
<manufacture of binding agent>
Ion exchange water 70 parts, dodecylbenzene sodium sulfonate 0.4 is put in the reactor possess blender Part and potassium peroxydisulfate 0.3 part, carry out being obtained by mixing mixture, be warming up to 60 DEG C.
On the other hand, hybrid ionic exchanged water 50 parts, dodecylbenzene sodium sulfonate 0.8 in another container Part, 2-EHA 67 parts, acrylonitrile 30 parts, glycidyl methacrylate 3 parts, Obtain monomer mixture.
This monomer mixture was added continuously in said mixture through 4 hours so that it is polymerization.Continuously In adding procedure, the temperature of reaction system is maintained 60 DEG C, is reacted.Add continuously after terminating, enter One step continues reaction 3 hours at 70 DEG C, and (binding agent is water-dispersible to obtain the aqueous dispersions containing binding agent Liquid).
After the binding agent aqueous dispersions obtained is cooled to 25 DEG C, being added to ammonia by pH regulator is 7, It is then introduced into steam and removes unreacted monomer.Then, relative to the solid constituent 100 parts of binding agent, Add ethylenediaminetetraacetic acid 0.25 part immediately, they are mixed, carries out further with ion exchange water The adjustment of solid component concentration, is carried out with the stainless steel metal gauze of 200 mesh (mesh about 77 μm) Filter, obtain perforated membrane binding agent water-dispersible of mean diameter 100nm, solid component concentration 40% Liquid.
Vinyl monomer (the Glycidyl methacrylate with heat cross-linking group in perforated membrane binding agent Glyceride) polymerized unit containing ratio be 3%, the containing of the polymerized unit of (methyl) acrylate monomer Ratio is 67%, the polymerized unit of 'alpha ', ' bela '-unsaturated nitrile monomer be 30% containing ratio.
(embodiment 6)
Replace the non-conductive organic granular obtained in the operation (1) of embodiment 1～(3), use following non- Electric conductivity organic granular has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, Obtain organic dividing plate of band perforated membrane and secondary cell and evaluated.Result is as shown in table 1.
<manufacture of non-conductive organic granular>
The moisture of the seeding polymerization composition granule B obtained in operation (2) is put in the reactor possess blender A prose style free from parallelism 10 parts (in terms of solid constituent benchmark, i.e. with the weight basis of seeding polymerization composition granule B), list Body mixture (divinylbenzene and the mixture of 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, benzene second Alkene sulfonic acid 1.2 parts, dodecylbenzene sodium sulfonate 1.0 parts, peroxidating-2-ethyl hexyl as polymerization initiator Tert-butyl acrylate (You company system, trade name: Perbutyl O) 5 parts and ion exchange water 200 parts, Stir 12 hours at 35 DEG C, thus make seeding polymerization composition granule B fully absorb monomer mixture and polymerization is drawn Send out agent.Then, it is polymerized 4 hours at 90 DEG C.Then, import steam and remove unreacted monomer.
Thus, the aqueous dispersion of the non-conductive organic granular of mean diameter 0.4 μm is obtained.
Formed from seed polymer granule and start to obtaining the monomer that used non-conductive organic granular The composition of (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and styrene sulfonic acid), with And the heat resisting temperature (T10 value) of non-conductive organic granular, binding agent can be with heat cross-linking group (ring Epoxide) content of functional group's (sulfonic group) that cross-links and metals content impurity as shown in table 1.
(embodiment 7)
Replace the non-conductive organic granular obtained in the operation (1) of embodiment 1～(3), use following non- Electric conductivity organic granular has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, Obtain organic dividing plate of band perforated membrane and secondary cell and evaluated.Result is as shown in table 1.
<manufacture of non-conductive organic granular>
The moisture of the seeding polymerization composition granule B obtained in operation (2) is put in the reactor possess blender A prose style free from parallelism 10 parts (in terms of solid constituent benchmark, i.e. with the weight basis of seeding polymerization composition granule B), list Body mixture (divinylbenzene and the mixture of 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, methyl Allyl sulphonic acid 0.6 part, dodecylbenzene sodium sulfonate 1.0 parts, peroxidating-2-as polymerization initiator Ethylhexanate (You company system, trade name: Perbutyl O) 5 parts and ion exchange water 200 Part, stir 12 hours at 35 DEG C, thus make seeding polymerization composition granule B fully absorb monomer mixture And polymerization initiator.Then, it is polymerized 4 hours at 90 DEG C.Then, import steam and remove the most anti- The monomer answered.
Thus, the aqueous dispersion of the non-conductive organic granular of mean diameter 0.4 μm is obtained.
Formed from seed polymer granule and start to obtaining the monomer that used non-conductive organic granular The composition of (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and methallylsulfonic acid), And the heat resisting temperature (T10 value) of non-conductive organic granular, binding agent can be with heat cross-linking group (ring Epoxide) content of functional group's (sulfonic group) that cross-links and metals content impurity as shown in table 1.
(embodiment 8)
Replace the non-conductive organic granular obtained in the operation (1) of embodiment 1～(3), use following non- Electric conductivity organic granular has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, Obtain organic dividing plate of band perforated membrane and secondary cell and evaluated.Result is as shown in table 1.
<manufacture of non-conductive organic granular>
The moisture of the seeding polymerization composition granule B obtained in operation (2) is put in the reactor possess blender A prose style free from parallelism 10 parts (in terms of solid constituent benchmark, i.e. with the weight basis of seeding polymerization composition granule B), list Body mixture (divinylbenzene and the mixture of 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, phosphoric acid -2-(methyl) acryloyloxyethyl ester 1.3 parts, dodecylbenzene sodium sulfonate 1.0 parts, as polymerization initiator Peroxide-2-ethyl hexanoic acid tert-butyl (You company system, trade name: Perbutyl O) 5 parts and ion Exchanged water 200 parts, stirs 12 hours at 35 DEG C, thus makes seeding polymerization composition granule B fully absorb Monomer mixture and polymerization initiator.Then, it is polymerized 4 hours at 90 DEG C.Then, steaming is imported Gas removes unreacted monomer.
Thus, the aqueous dispersion of the non-conductive organic granular of mean diameter 0.4 μm is obtained.
Formed from seed polymer granule and start to obtaining the monomer that used non-conductive organic granular (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and phosphoric acid-2-(methyl) acryloyl-oxy Base ethyl ester) composition and the heat resisting temperature (T10 value) of non-conductive organic granular, binding agent can The content of the functional group's (phosphate) cross-linked with heat cross-linking group (epoxy radicals) and metals content impurity such as table 1 Shown in.
(embodiment 9)
Replace the perforated membrane binding agent obtained in the operation (4) of embodiment 1, use following perforated membrane to use Binding agent has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, obtains Organic dividing plate with perforated membrane and secondary cell are also evaluated.Result is as shown in table 1.
<manufacture of binding agent>
Ion exchange water 70 parts, dodecylbenzene sodium sulfonate 0.4 is put in the reactor possess blender Part and potassium peroxydisulfate 0.3 part, carry out being obtained by mixing mixture, be warming up to 60 DEG C.
On the other hand, hybrid ionic exchanged water 50 parts, dodecylbenzene sodium sulfonate 0.8 in another container Part, 2-EHA 78 parts, acrylonitrile 20.5 parts, allyl glycidyl ether 1.5 parts, To monomer mixture.
This monomer mixture was added continuously in said mixture through 4 hours so that it is polymerization.Continuously In adding procedure, the temperature of reaction system is maintained 60 DEG C, is reacted.Add continuously after terminating, enter One step continues reaction 3 hours at 70 DEG C, and (binding agent is water-dispersible to obtain the aqueous dispersions containing binding agent Liquid).
After the binding agent aqueous dispersions obtained is cooled to 25 DEG C, being added to ammonia by pH regulator is 7, It is then introduced into steam and removes unreacted monomer.Then, relative to the solid constituent 100 parts of binding agent, Add ethylenediaminetetraacetic acid 0.25 part immediately, they are mixed, carries out further with ion exchange water The adjustment of solid component concentration, is carried out with the stainless steel metal gauze of 200 mesh (mesh about 77 μm) Filter, obtain perforated membrane binding agent water-dispersible of mean diameter 100nm, solid component concentration 40% Liquid.
Vinyl monomer (the allyl glycidol with heat cross-linking group in perforated membrane binding agent Ether) polymerized unit containing ratio be 1.5%, the polymerized unit of (methyl) acrylate monomer containing than Rate is 78%, the polymerized unit of 'alpha ', ' bela '-unsaturated nitrile monomer be 20.5% containing ratio.
(embodiment 10)
Replace the perforated membrane binding agent obtained in the operation (4) of embodiment 1, use following perforated membrane to use Binding agent has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, obtains Organic dividing plate with perforated membrane and secondary cell are also evaluated.Result is as shown in table 1.
<manufacture of binding agent>
Ion exchange water 70 parts, dodecylbenzene sodium sulfonate 0.4 is put in the reactor possess blender Part and potassium peroxydisulfate 0.3 part, carry out being obtained by mixing mixture, be warming up to 60 DEG C.
On the other hand, hybrid ionic exchanged water 50 parts, dodecylbenzene sodium sulfonate 0.8 in another container Part, 2-EHA 77.5 parts, acrylonitrile 20 parts, 3-methacryloxy triethoxysilicane 2.5 parts of alkane, obtains monomer mixture.
This monomer mixture was added continuously in said mixture through 4 hours so that it is polymerization.Continuously In adding procedure, the temperature of reaction system is maintained 60 DEG C, is reacted.Add continuously after terminating, enter One step continues reaction 3 hours at 70 DEG C, and (binding agent is water-dispersible to obtain the aqueous dispersions containing binding agent Liquid).
After the binding agent aqueous dispersions obtained is cooled to 25 DEG C, being added to ammonia by pH regulator is 7, It is then introduced into steam and removes unreacted monomer.Then, relative to the solid constituent 100 parts of binding agent, Add ethylenediaminetetraacetic acid 0.25 part immediately, they are mixed, carries out further with ion exchange water The adjustment of solid component concentration, is carried out with the stainless steel metal gauze of 200 mesh (mesh about 77 μm) Filter, obtain perforated membrane binding agent water-dispersible of mean diameter 100nm, solid component concentration 40% Liquid.
Vinyl monomer (the 3-methacryloxy with heat cross-linking group in perforated membrane binding agent Triethoxysilane) polymerized unit containing ratio be 2.5%, the polymerization list of (methyl) acrylate monomer Unit containing ratio be 77.5%, the polymerized unit of 'alpha ', ' bela '-unsaturated nitrile monomer be 20% containing ratio.
(embodiment 11)
Replace the non-conductive organic granular obtained in the operation (1) of embodiment 1～(3), use following non- Electric conductivity organic granular has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, Obtain organic dividing plate of band perforated membrane and secondary cell and evaluated.Result is as shown in table 1.
<manufacture of non-conductive organic granular>
The moisture of the seeding polymerization composition granule B obtained in operation (2) is put in the reactor possess blender A prose style free from parallelism 10 parts (in terms of solid constituent benchmark, i.e. with the weight basis of seeding polymerization composition granule B), list Body mixture (divinylbenzene and the mixture of 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, 2-third Acrylamide-2-methyl propane sulfonic acid 4.5 parts, dodecylbenzene sodium sulfonate 1.0 parts, mistake as polymerization initiator Oxidation-2 ethyl hexanoic acid the tert-butyl ester (You company system, trade name: Perbutyl O) 5 parts and ion exchange 200 parts of water, stirs 12 hours at 35 DEG C, thus makes seeding polymerization composition granule B fully absorb monomer Mixture and polymerization initiator.Then, it is polymerized 4 hours at 90 DEG C.Then, import steam to remove Remove unreacted monomer.
Thus, the aqueous dispersion of the non-conductive organic granular of mean diameter 0.4 μm is obtained.
Formed from seed polymer granule and start to obtaining the monomer that used non-conductive organic granular (styrene, methacrylic acid, divinylbenzene, vinyl xylene, ethyl vinyl benzene and 2-acrylamide-2-methyl-prop sulphur Acid) composition and the heat resisting temperature (T10 value) of non-conductive organic granular, binding agent can be with heat The content of functional group's (sulfonic group) that crosslinkable groups (epoxy radicals) cross-links and metals content impurity such as table 1 institute Show.
(embodiment 12)
Replace the perforated membrane binding agent obtained in the operation (4) of embodiment 1, use following perforated membrane to use Binding agent has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, obtains Organic dividing plate with perforated membrane and secondary cell are also evaluated.Result is as shown in table 1.
<manufacture of binding agent>
Ion exchange water 70 parts, dodecylbenzene sodium sulfonate 0.4 is put in the reactor possess blender Part and potassium peroxydisulfate 0.3 part, carry out being obtained by mixing mixture, be warming up to 60 DEG C.
On the other hand, hybrid ionic exchanged water 50 parts, dodecylbenzene sodium sulfonate 0.8 in another container Part, 2-EHA 75 parts, acrylonitrile 17 parts, glycidyl methacrylate 8 parts, Obtain monomer mixture.
This monomer mixture was added continuously in said mixture through 4 hours so that it is polymerization.Continuously In adding procedure, the temperature of reaction system is maintained 60 DEG C, is reacted.Add continuously after terminating, enter One step continues reaction 3 hours at 70 DEG C, and (binding agent is water-dispersible to obtain the aqueous dispersions containing binding agent Liquid).
After the binding agent aqueous dispersions obtained is cooled to 25 DEG C, being added to ammonia by pH regulator is 7, It is then introduced into steam and removes unreacted monomer.Then, relative to the solid constituent 100 parts of binding agent, Add ethylenediaminetetraacetic acid 0.25 part immediately, they are mixed, carries out further with ion exchange water The adjustment of solid component concentration, is carried out with the stainless steel metal gauze of 200 mesh (mesh about 77 μm) Filter, obtain perforated membrane binding agent water-dispersible of mean diameter 100nm, solid component concentration 40% Liquid.
Vinyl monomer (the Glycidyl methacrylate with heat cross-linking group in perforated membrane binding agent Glyceride) polymerized unit containing ratio be 8%, the containing of the polymerized unit of (methyl) acrylate monomer Ratio is 75%, the polymerized unit of 'alpha ', ' bela '-unsaturated nitrile monomer be 17% containing ratio.
(embodiment 13)
Replace the perforated membrane binding agent obtained in the operation (4) of embodiment 1, use following perforated membrane to use Binding agent has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, obtains Organic dividing plate with perforated membrane and secondary cell are also evaluated.Result is as shown in table 1.
<manufacture of binding agent>
Styrene 5 parts, butadiene 10 parts, polyoxyethylene alkyl ether (flower king's strain is added in polymerization tank A Formula commercial firm Emulgen1150S-60) 3 parts and ion exchange water 70 parts, it is sufficiently stirred for.Then, will Temperature is set to 70 DEG C, adds water-soluble azo polymerization initiator (and the Wako Pure Chemical Industries as polymerization initiator VA-086 processed) 0.3 part and ion exchange water 10 parts, stir 120 minutes.
On the other hand, another polymerization tank B adds styrene 45.8 parts, butadiene 36.9 parts, methyl Glycidyl acrylate 2.3 parts, polyoxyethylene alkyl ether 10 parts and ion exchange water 30 parts also stir Mix, made emulsion.
Then, by the emulsion of making through about 300 minutes after polymerization tank B is added continuously to polymerization tank A, Stir about 180 minutes, cools down when monomer consumption reaches 95%, terminates reaction.Thus, To solid component concentration be 40%, individual number average particle diameter be perforated membrane binding agent water-dispersible of 150nm Liquid.
Vinyl monomer (the Glycidyl methacrylate with heat cross-linking group in perforated membrane binding agent Glyceride) polymerized unit containing ratio be 2.3%, the polymerized unit of (methyl) acrylate monomer and The polymerized unit of 'alpha ', ' bela '-unsaturated nitrile monomer is 0% containing ratio.
(embodiment 14)
With completely on the face of the negative electrode active material layer side of the negative pole obtained in the operation (7) of embodiment 1 Covering negative electrode active material layer and the mode coating Examples 1 that dried perforated membrane thickness is 5 μm The perforated membrane slurry obtained in operation (5), obtains pulp layer.Pulp layer is dried 10 minutes at 50 DEG C, Form perforated membrane, obtain the negative pole of band perforated membrane.The negative pole of the band perforated membrane obtained has (perforated membrane)/(negative Pole active material layer)/(Copper Foil) such layer composition.To the flexibility of the negative pole of the band perforated membrane obtained, fall Mealiness and water quantities are evaluated.Result is as shown in table 1.
Replace organic dividing plate of the band perforated membrane obtained in the operation (8) of embodiment 1, employ organic dividing plate (operation (8) of the polypropylene dividing plate of monolayer, the porosity 55%, thickness 25 μm and embodiment 1 is used The dividing plate making organic dividing plate is identical).
It addition, replace the negative pole obtained in the operation (7) of embodiment 1, employ the negative of above-mentioned band perforated membrane Pole, in addition, carries out operation similarly to Example 1, has obtained secondary cell and evaluated. Result is as shown in table 1.It should be noted that the negative pole of circular band perforated membrane is positioned in exterior package container Time interior, with the face of its perforated membrane side towards circular organic dividing plate side, the face of Copper Foil side is towards upper The mode of side loads.
(embodiment 15)
<making of the NMP dispersion of non-conductive granule>
100 parts of (solid constituents of the aqueous dispersion of the non-conductive granule obtained in the operation (3) of embodiment 1 Concentration is 20%) in add METHYLPYRROLIDONE (NMP) 200 parts and be sufficiently mixed after, subtract at 90 DEG C The water being distilled off in system under pressure ring border and NMP, obtain non-conductive granule NMP dispersion (Gu Body constituent concentration is 20%).
<making of the NMP dispersion of binding agent>
(solid becomes the aqueous dispersion of the perforated membrane binding agent obtained in the operation (4) of embodiment 1 100 parts Be divided into 40%) in add 760 parts of NMP and after being sufficiently mixed, under 90 DEG C of reduced pressure atmosphere in removing system Water and NMP, obtain the NMP dispersion (solid constituent is 10%) of perforated membrane binding agent.
<manufacture of perforated membrane slurry>
By the NMP dispersion of non-conductive granule obtained in above-mentioned operation and perforated membrane binding agent NMP dispersion mixes with solid constituent than the mode as 87:13, obtains solid component concentration more than 18% Pore membrane slurry.
<manufacture of the negative pole of band perforated membrane>
With completely on the face of the negative electrode active material layer side of the negative pole obtained in the operation (7) of embodiment 1 Covering negative electrode active material layer and the mode that dried perforated membrane thickness is 5 μm are coated with in above-mentioned operation The perforated membrane slurry obtained, obtains pulp layer.Being dried 10 minutes at 100 DEG C by pulp layer, formation is many Pore membrane, obtains the negative pole of band perforated membrane.The negative pole of the band perforated membrane obtained has (perforated membrane)/(negative electrode active Material layer)/(Copper Foil) such layer composition.To the flexibility of negative pole of the band perforated membrane obtained, powder falling and Water quantities is evaluated.Result is as shown in table 1.
<there is the manufacture of the secondary cell of the negative pole of band perforated membrane>
Replace organic dividing plate of the band perforated membrane obtained in the operation (8) of embodiment 1, employ organic dividing plate (operation (8) of the polypropylene dividing plate of monolayer, the porosity 55%, thickness 25 μm and embodiment 1 is used The dividing plate making organic dividing plate is identical).
It addition, replace the negative pole obtained in the operation (7) of embodiment 1, employ the negative of above-mentioned band perforated membrane Pole, in addition, carries out operation similarly to Example 1, has obtained secondary cell and evaluated. Result is as shown in table 1.It should be noted that the negative pole of circular band perforated membrane is positioned in exterior package container Time interior, with the face of its perforated membrane side towards circular organic dividing plate side, the face of Copper Foil side is towards upper The mode of side loads.
(comparative example 1)
Replace the perforated membrane binding agent obtained in the operation (4) of embodiment 1, use following perforated membrane to use Binding agent has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, obtains Organic dividing plate with perforated membrane and secondary cell are also evaluated.Result is as shown in table 1.
<manufacture of binding agent>
Ion exchange water 70 parts, dodecylbenzene sodium sulfonate 0.4 is put in the reactor possess blender Part and potassium peroxydisulfate 0.3 part, carry out mixing and mixture, be warming up to 60 DEG C.
On the other hand, hybrid ionic exchanged water 50 parts, dodecylbenzene sodium sulfonate 0.8 in another container Part, 2-EHA 79 parts, acrylonitrile 21 parts, obtain monomer mixture.
This monomer mixture was added continuously in said mixture through 4 hours so that it is polymerization.Continuously In adding procedure, the temperature of reaction system is maintained 60 DEG C, is reacted.Add continuously after terminating, enter One step continues reaction 3 hours at 70 DEG C, and (binding agent is water-dispersible to obtain the aqueous dispersions containing binding agent Liquid).
After the binding agent aqueous dispersions obtained is cooled to 25 DEG C, being added to ammonia by pH regulator is 7, It is then introduced into steam and removes unreacted monomer.Then, relative to the solid constituent 100 parts of binding agent, Add ethylenediaminetetraacetic acid 0.25 part immediately, they are mixed, carries out further with ion exchange water The adjustment of solid component concentration, is carried out with the stainless steel metal gauze of 200 mesh (mesh about 77 μm) Filter, obtain perforated membrane binding agent water-dispersible of mean diameter 100nm, solid component concentration 40% Liquid.
Containing of the polymerized unit of the vinyl monomer with heat cross-linking group in perforated membrane binding agent Ratio is 0%, the polymerized unit of (methyl) acrylate monomer containing ratio be 79%, α, β-unsaturation The polymerized unit of nitrile monomer is 21% containing ratio.
(comparative example 2)
Replace the non-conductive organic granular obtained in the operation (1) of embodiment 1～(3), use following non- Electric conductivity organic granular has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, Obtain organic dividing plate of band perforated membrane and secondary cell and evaluated.Result is as shown in table 1.
<manufacture of non-conductive organic granular>
The moisture of the seeding polymerization composition granule B obtained in operation (2) is put in the reactor possess blender A prose style free from parallelism 10 parts (in terms of solid constituent benchmark, i.e. with the weight basis of seeding polymerization composition granule B), list Body mixture (divinylbenzene and the mixture of 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, dodecane Base benzene sulfonic acid sodium salt 1.0 parts, as polymerization initiator peroxide-2-ethyl hexanoic acid tert-butyl (You company system, Trade name: Perbutyl O) 5 parts and ion exchange water 200 parts, stir 12 hours at 35 DEG C, by This makes seeding polymerization composition granule B fully absorb monomer mixture and polymerization initiator.Then, by it 90 It is polymerized 4 hours at DEG C.Then, import steam and remove unreacted monomer.
Thus, the aqueous dispersion of the non-conductive organic granular of mean diameter 0.4 μm is obtained.
Formed from seed polymer granule and start to obtaining the monomer that used non-conductive organic granular The composition of (styrene, methacrylic acid, divinylbenzene and vinyl xylene, ethyl vinyl benzene) and non-conductive have The heat resisting temperature (T10 value) of machine granule and metals content impurity are as shown in table 1.
(comparative example 3)
Replace the perforated membrane binding agent obtained in the operation (4) of embodiment 1, use following perforated membrane to use Binding agent has manufactured perforated membrane slurry, in addition, carries out operation similarly to Example 1, obtains Organic dividing plate with perforated membrane and secondary cell are also evaluated.Result is as shown in table 1.
<manufacture of binding agent>
Styrene 5 parts, butadiene 10 parts, polyoxyethylene alkyl ether (flower king's strain is added in polymerization tank A Formula commercial firm Emulgen1150S-60) 3 parts and ion exchange water 70 parts, it is sufficiently stirred for.Then, will Temperature is set to 70 DEG C, adds water-soluble azo polymerization initiator (and the Wako Pure Chemical Industries as polymerization initiator VA-086 processed) 0.3 part and ion exchange water 10 parts, stir 120 minutes.
On the other hand, another polymerization tank B adds styrene 47 parts, butadiene 38 parts, polyoxy second 10 parts of allylic alkylation ether and ion exchange water 30 parts are also stirred, and have made emulsion.
Then, by the emulsion of making through about 300 minutes after polymerization tank B is added continuously to polymerization tank A, Stir about 180 minutes, cools down when monomer consumption reaches 95%, terminates reaction.Thus obtain The aqueous dispersions of perforated membrane binding agent that solid component concentration is 40%, individual number average particle diameter is 150nm.
Containing of the polymerized unit of the vinyl monomer with heat cross-linking group in perforated membrane binding agent Ratio, poly-containing ratio and 'alpha ', ' bela '-unsaturated nitrile monomer of polymerized unit of (methyl) acrylate monomer That closes unit is 0% containing ratio.
(comparative example 4)
The non-conductive organic granular obtained in the operation (1) of replacement embodiment 1～(3), uses Sumitomo Chemical The Alumana AKP-50 (mean diameter 0.3 μm) that company manufactures has manufactured perforated membrane slurry, in addition, Carry out operation similarly to Example 1, obtained organic dividing plate of band perforated membrane and secondary cell and carried out Evaluate.Result is as shown in table 1.
[table 1]
By the result deducibility the description below of table 1.
There is the secondary cell perforated membrane using following secondary cell perforated membrane slurry (embodiment 1～15) to be formed Secondary battery separator and the flexibility of electrode for secondary battery, powder falling excellent, described secondary cell porous Film slurry (embodiment 1～15) comprises: comprise the polymerized unit of the vinyl monomer with heat cross-linking group Binding agent and have can be with the non-conductive organic granular of functional group of this heat cross-linking group crosslinking. Further, water quantities contained in above-mentioned perforated membrane is few, and tenor is few.Its result, can suppress secondary electricity Side reaction in pond, makes the battery behaviors such as cycle characteristics improve.Wherein, there is the following secondary cell of use The secondary battery separator of the secondary cell perforated membrane that perforated membrane slurry (embodiment 1～7 and 14,15) is formed And the flexibility of electrode for secondary battery, powder falling are the most excellent, moisture in perforated membrane and tenor are also Few, demonstrate the cycle characteristics of excellence, described secondary cell perforated membrane slurry (embodiment 1～7 and 14, 15) comprise: comprise and there is sulfonic group as the non-conductive organic granular of hydrophilic acidic group and have Epoxy radicals is as the binding agent of the functional group that can cross-link with hydrophilic acidic group.
On the other hand, use the situation (comparative example 1,3) of the binding agent without heat cross-linking group, make Can be with the situation (ratio of the non-conductive organic granular of the functional group of heat cross-linking group crosslinking with not having Relatively example 2) and use inorganic particle (aluminium oxide) to replace the situation (comparative example 4) of non-conductive organic granular Under, secondary battery separator and the flexibility of electrode for secondary battery, powder falling are poor, therefore cycle characteristics deterioration. Wherein, inorganic particle (aluminium oxide) is used to replace in the situation (comparative example 4) of non-conductive organic granular, many Water quantities contained in pore membrane is many, and the content of metal impurities is many, and therefore, cycle characteristics is particularly poor.

Claims (10)

1. a secondary cell perforated membrane slurry, comprising:
Comprise the binding agent of the polymerized unit of the vinyl monomer with heat cross-linking group,
There is the non-conductive organic granular of the functional group that can cross-link with this heat cross-linking group, and
Solvent,
Wherein, described binding agent is possibly together with the polymerized unit of (methyl) acrylate monomer and α, β-unsaturation The polymerized unit of nitrile monomer,
In whole polymerized units, described in there is the polymerized unit of vinyl monomer of heat cross-linking group Be 0.1～10 mass % containing ratio, the polymerized unit of described (methyl) acrylate monomer containing ratio Being 50～98 mass %, described α, the polymerized unit of alpha, beta-unsaturated nitriles monomer is 1.0～40 matter containing ratio Amount %.
Secondary cell perforated membrane slurry the most according to claim 1, wherein,
Described heat cross-linking group is epoxy radicals or pi-allyl.
Secondary cell perforated membrane slurry the most according to claim 1 and 2, wherein,
The mean diameter of described non-conductive organic granular is 0.1～2.0 μm, and
When heating with programming rate 10 DEG C/min under nitrogen atmosphere with thermobalance, described non-conductive organic It is more than 250 DEG C that the loss of weight ratio of granule reaches the temperature of 10 mass %.
Secondary cell perforated membrane slurry the most according to claim 1 and 2, wherein,
Relative to non-conductive organic granular, described can be with the containing of the functional group of heat cross-linking group crosslinking Amount is 0.008～0.240mmol/g.
Secondary cell perforated membrane slurry the most according to claim 1 and 2, wherein,
Described can be sulfonic group or phosphate with the functional group of heat cross-linking group crosslinking.
6. a secondary cell perforated membrane, it is by by the secondary according to any one of Claims 1 to 5 Battery perforated membrane slurry is formed as membranaceous and dry and obtains.
7. a secondary cell perforated membrane, comprising:
Comprise the binding agent of the polymerized unit of the vinyl monomer with heat cross-linking group, and
There is the non-conductive organic granular of the functional group that can cross-link with this heat cross-linking group,
Wherein, between described binding agent and described non-conductive organic granular, there is cross-linked structure,
Described binding agent is possibly together with the polymerized unit of (methyl) acrylate monomer and 'alpha ', ' bela '-unsaturated nitrile monomer Polymerized unit,
In whole polymerized units, described in there is the polymerized unit of vinyl monomer of heat cross-linking group Be 0.1～10 mass % containing ratio, the polymerized unit of described (methyl) acrylate monomer containing ratio Being 50～98 mass %, described α, the polymerized unit of alpha, beta-unsaturated nitriles monomer is 1.0～40 matter containing ratio Amount %.
8. an electrode for secondary battery, comprising:
Collector body,
Electrode active material layer, it is attached to this collector body and comprises electrode active material and electrode bonding Agent, and
The secondary cell porous described in claim 6 or 7 being stacked on this electrode active material layer surface Film.
9. a secondary battery separator, comprising:
Organic dividing plate, and
The secondary cell perforated membrane described in claim 6 or 7 being stacked on this organic dividing plate.
10. a secondary cell, comprising:
Positive pole, negative pole, organic dividing plate and electrolyte,
Wherein, any superimposed layer in described positive pole, negative pole and organic dividing plate is had the right requirement 6 or 7 Described secondary cell perforated membrane.
CN201180057788.4A 2010-09-30 2011-09-30 Secondary cell perforated membrane slurry, secondary cell perforated membrane, electrode for secondary battery, secondary battery separator and secondary cell Active CN103238234B (en)

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