CN108878742A - Nonaqueous electrolytic solution secondary battery insulating properties porous layer - Google Patents

Nonaqueous electrolytic solution secondary battery insulating properties porous layer Download PDF

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Publication number
CN108878742A
CN108878742A CN201710333820.6A CN201710333820A CN108878742A CN 108878742 A CN108878742 A CN 108878742A CN 201710333820 A CN201710333820 A CN 201710333820A CN 108878742 A CN108878742 A CN 108878742A
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China
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secondary battery
electrolytic solution
nonaqueous electrolytic
solution secondary
porous layer
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Chinese (zh)
Inventor
绪方俊彦
铃木纯次
桥胁弘树
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority to CN201710333820.6A priority Critical patent/CN108878742A/en
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)

Abstract

Problem of the present invention is that improving the productivity of nonaqueous electrolytic solution secondary battery.Nonaqueous electrolytic solution secondary battery of the invention insulating properties porous layer, it contains the thermoplastic resin for constituting nonaqueous electrolytic solution secondary battery lamination spacer, voidage is 25% or more and 80% hereinafter, under conditions of 25 DEG C, 30kN, 1 minute × 2 times, and with 92：2.7：5.3 quality ratio includes that the peel strength when nonaqueous electrolytic solution secondary battery of electrode active material, conductive agent and binder is crimped with electrode is greater than 0N/m and 2.0N/m or less.

Description

Nonaqueous electrolytic solution secondary battery insulating properties porous layer
Technical field
The present invention relates between nonaqueous electrolytic solution secondary battery insulating properties porous layer, nonaqueous electrolytic solution secondary battery stacking Spacing body, nonaqueous electrolytic solution secondary battery component and nonaqueous electrolytic solution secondary battery.
Background technique
Currently, the nonaqueous electrolytic solution secondary batteries such as lithium secondary battery are as personal computer, mobile phone and mobile letter It ceases battery or vehicle battery used in the machines such as terminal and is widely used.
As the spacer in this nonaqueous electrolytic solution secondary battery, it is known that in the porous base using polyolefin as principal component Lamination spacer obtained by the porous layer containing filler and resin is laminated in at least one side of material.
For example, in patent document 1, filler will be contained and using aromatic polyamide resin as the heat-resisting of main body by describing Property porous layer is layered in non-aqueous secondary battery lamination spacer obtained by least one face of porous substrate.In addition, In patent document 2, describing will be containing the water-soluble polymer as adhesive and using filler as the heat-resisting porous of main body Layer stackup at least one face of porous substrate obtained by non-aqueous secondary battery lamination spacer.
In the assembling of nonaqueous electrolytic solution secondary battery, in order to improve the adaptation between electrode and spacer and to the two It is suppressed to crimp.Using patent document 1 for representative, stacking contain spacer obtained by porous layer of the resin as main body, On the one hand it shows high adaptation, and on the other hand has the problem that air permeability is low thus battery behavior is not high enough.On the other hand, Using patent document 2 for representative, stacking contain spacer obtained by porous layer of the filler as main body, on the one hand show high Air permeability, and the position deviation of electrode and spacer is on the other hand generated when not having adaptation, battery assembly with electrode, battery is special Property reduce the problem of.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2009-21265 bulletin (on January 29th, 2009 is open)
Patent document 2：Japanese Unexamined Patent Publication 2009-224343 bulletin (on October 1st, 2009 is open)
Summary of the invention
Problem to be solved by the invention
When being suppressed at room temperature with electrode the object of the present invention is to provide one kind electrode between have adaptation, And the nonaqueous electrolytic solution secondary battery insulating properties porous layer with air permeability sufficiently high.
The means used to solve the problem
The present invention includes to invent shown in following [1]~[5].
[1] a kind of nonaqueous electrolytic solution secondary battery insulating properties porous layer, is used to cover composition non-aqueous electrolyte secondary The entire surface of at least one side of the porous substrate of battery lamination spacer, wherein
Above-mentioned nonaqueous electrolytic solution secondary battery insulating properties porous layer contains thermoplastic resin,
Voidage be 25% or more and 80% hereinafter,
Under conditions of 25 DEG C, 30kN, 1 minute × 2 times, and with 92：2.7：5.3 quality ratio contains electrode activity thing The peel strength when nonaqueous electrolytic solution secondary battery of matter, conductive agent and binder is crimped with electrode be greater than 0N/m and 2.0N/m following.
[2] the insulating properties porous layer of the nonaqueous electrolytic solution secondary battery as described in [1], wherein above-mentioned peel strength is 0.5N/m or more and 2.0N/m or less.
[3] a kind of nonaqueous electrolytic solution secondary battery lamination spacer has nonaqueous electrolytic solution described in [1] or [2] Secondary cell insulating properties porous layer and polyolefin micro porous polyolefin membrane.
[4] a kind of nonaqueous electrolytic solution secondary battery component, to configure in order described in any one of positive, [1] or [2] Nonaqueous electrolytic solution secondary battery insulating properties porous layer or [3] described in nonaqueous electrolytic solution secondary battery lamination spacer, And cathode forms.
[5] a kind of nonaqueous electrolytic solution secondary battery has nonaqueous electrolytic solution secondary battery described in [1] or [2] with absolutely Nonaqueous electrolytic solution secondary battery lamination spacer described in edge porous layer or [3].
Invention effect
Nonaqueous electrolytic solution secondary battery according to the present invention is played with insulating properties porous layer and is carried out at room temperature with electrode Have the effect of adaptation with electrode when compacting and there is air permeability sufficiently high.
Detailed description of the invention
Fig. 1 is the signal for showing the method for crimping porous layer of the invention and electrode under the conditions of 25 DEG C, 30kN Figure.
Fig. 2 is the schematic diagram for showing the method for measurement peel strength of the invention.
Specific embodiment
An embodiment of the invention is described as follows, however the present invention is not limited thereto.The present invention is not by following Each composition for illustrating limits, and can make various changes in range shown in the scope of the claims, for by different realities Embodiment obtained by disclosed technological means is appropriately combined respectively is applied in mode, technical scope of the invention is also contained in In.It should be noted that as long as no particularly pointing out in this specification, then it represents that " A~B " of numberical range mean that " A with Upper and B or less ".
[embodiment 1：Nonaqueous electrolytic solution secondary battery insulating properties porous layer]
Nonaqueous electrolytic solution secondary battery involved in embodiments of the present invention 1 is with insulating properties porous layer (hereinafter, also referred to as For " porous layer ") be for cover constitute nonaqueous electrolytic solution secondary battery lamination spacer porous substrate at least one side The nonaqueous electrolytic solution secondary battery of entire surface insulating properties porous layer, containing thermoplastic resin, voidage be 25% or more and 80% hereinafter, under conditions of 25 DEG C, 30kN, 1 minute × 2 times, and with 92：2.7：5.3 quality ratio contains electrode activity The peel strength when nonaqueous electrolytic solution secondary battery of substance, conductive agent and binder is crimped with electrode be greater than 0N/m and 2.0N/m following.
With 92：2.7：5.3 quality ratio contains the non-aqueous electrolyte secondary of electrode active material, conductive agent and binder Electrode for cell refers to the electrode with representative composition used in nonaqueous electrolytic solution secondary battery.Therefore, it can be said that this The porous layer with electrode with adaptation of embodiment, also has with general electrode used in nonaqueous electrolytic solution secondary battery There is adaptation.
The nonaqueous electrolytic solution secondary battery electrode of present embodiment is more specifically following electrode：It will be containing just Pole active material (CellSeedC-10N (Nippon Chemical Ind's system), LiCoO2, 10 μm of average grain diameter, real density 4.8g/cm3) 92 parts by weight, conductive agent (acetylene black (Deuki Kagaku Kogyo Co., Ltd's system), real density 2.2g/cm3) 2.7 weight Part, binder 1 (PTFE31-JR (three well Du Pont fluorine chemistry Co. Ltd. systems), real density 2.2g/cm3) 4.55 parts by weight, viscous Tie agent 2 (Serogen4H (Di-ichi Kogyo Seiyaku Co., Ltd.'s system), real density 1.4g/cm3) 0.75 parts by weight and water viscosity The mixture of 2700 ± 1000cp is coated on 20 μm of thickness and not on the aluminium foil in gap, after dry, is calendered to by roll-in method Coated film with a thickness of 140 μm of (apparent density 3.5g/cm3) obtained from electrode.
If being illustrated to " being crimped under conditions of 30kN, 1 minute × 2 times with electrode " in this specification, As follows.That is, porous layer or lamination spacer comprising the porous layer and electrode are laminated so that porous layer and electrode Contact is to form laminated body.Then, in the laminated body, to the opposite face in the face of porous layer and contact electrode (hereinafter, claiming For " opposite face ") pressure 1 minute of the uniformly applied 30kN of entire surface.After 1 minute, temporarily carry out except lotus, then immediately Again to pressure 1 minute of the uniformly applied 30kN of entire surface of the above-mentioned opposite face of the laminated body." in 30kN, 1 minute Crimped under conditions of × 2 times with electrode " mean above a series of movement.
Here, Fig. 1 shows be to show with electrode to crimp porous layer of the invention under conditions of 25 DEG C, 30kN Method an example schematic diagram.
In Fig. 1,1a indicates that desk-top pressuring machine, 1b indicate desk-top pressuring machine, and 2 indicate polyethylene terephthalate (PET) film, 3 indicate measurement sample (size：25mm × 80mm), 4 indicate electrode, and 5 indicate polyethylene terephthalate (PET) film.The breakage of electrode 4, measurement sample 3 in order to prevent, preferably above-mentioned crimping are used in desk-top pressuring machine 1a and measurement Sandwiched PET film 2 and the sandwiched polyethylene terephthalate between desk-top pressuring machine 1b and electrode 4 between sample 3 (PET) film 5 carries out.
Measurement sample 3 in Fig. 1 is equivalent to above-mentioned " porous layer or the lamination spacer comprising the porous layer ".In addition, Measurement sample 3 and electrode 4 are laminated in a contact fashion (that is, make measurement sample 3 with electrode 4 while Be overlapped) and formed be above-mentioned " laminated body ".In addition, the upper surface of measurement sample 3 in Fig. 1 (face of setting PET film 2) and electricity (contact surface of electrode 4 and PET film 5) is equivalent to above-mentioned " opposite face " below pole 4.
The method of pressure about the uniformly applied 30kN of entire surface to above-mentioned opposite face, specifically, for example, can lift The desk-top pressuring machine bigger than the opposite face area is used out, to the method for the uniformly applied pressure of the entire surface of the opposite face.
In addition, temporarily carrying out and then applying stressed method again, specifically except lotus about after applying pressure 1 minute For, for example, can enumerate makes pressuring machine squeeze above-mentioned opposite face after applying pressure (pressurizeing for the first time), temporarily make the pressuring machine It is left from the opposite face, and then the pressuring machine is made to squeeze the opposite face again and apply the method for pressure (second pressurize). It should be noted that the time between second of pressurization, pressuring machine leaves from opposite face of pressurizeing for the first time is set as less than 120 The short time of second.
Porous layer involved in an embodiment of the invention can be used as the component for constituting nonaqueous electrolytic solution secondary battery It uses, preferably as constituting nonaqueous electrolytic solution secondary battery layer involved in aftermentioned an embodiment of the invention The component of folded spacer come using.That is, non-by the way that porous layer involved in an embodiment of the invention is layered in composition The one or both sides of the polyolefin porous membrane (hereinafter also referred to as " porous substrate ") of water electrolysis liquid secondary battery lamination spacer On, so as to form nonaqueous electrolytic solution secondary battery lamination spacer involved in an embodiment of the invention.
Porous layer involved in an embodiment of the invention is constituting nonaqueous electrolytic solution secondary battery stacking interval In the case where part, the entire surface of at least one side of porous substrate is covered.
In the case where there is the position not covered by porous layer on porous substrate, capped position and uncovered The ion permeability at position generates difference, as a result, the risk for having the cycle characteristics of electrode degradation, battery to reduce.In addition, depositing At uncovered position, nonaqueous electrolytic solution secondary battery lamination spacer and electrode can not be made equably closely sealed, therefore There are them to generate the risk of positional shift.In addition, when porous layer is the porous layer of heat resistance, nonaqueous electrolytic solution secondary battery layer When folded spacer is exposed to high temperature, from the thermal contraction of the above-mentioned position porous substrate for not having to be covered by porous layer, have non- The risk of the reduced performance of water electrolysis liquid secondary battery lamination spacer.It is porous involved in an embodiment of the invention Layer, by cover porous substrate at least one side entire surface, so as to make ion permeability homogenization, make with it is interelectrode It is closely sealed to become to be suitable for and prevent the generation of above-mentioned thermal contraction.
Porous layer involved in an embodiment of the invention contains thermoplastic resin.Porous layer, which is formed in inside, to be had The structure that multiple micropores and these micropores are concatenated is the layer that gas or liquid can pass through from one towards another side.In addition, Porous layer involved in an embodiment of the invention is as the structure for constituting nonaqueous electrolytic solution secondary battery lamination spacer Part in use, above-mentioned porous layer as the lamination spacer outermost layer and become the layer contacted with electrode.
< thermoplastic resin >
Thermoplastic resin contained by porous layer involved in an embodiment of the invention in the electrolyte of battery not It is molten, additionally, it is preferred that be electrochemically stable in the use scope of its battery.As above-mentioned thermoplastic resin, specifically, For example, can enumerate：The polyolefin such as polyethylene, polypropylene, polybutene and ethylene-propylene copolymer；Kynoar (PVDF), Polytetrafluoroethylene (PTFE), vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro alkyl Vinyl ether co-polymer, skewed segregation, vinylidene-trifluoro-ethylene copolymer, vinylidene-trichlorine Ethylene copolymer, vinylidene-ethylene fluoride base co-polymer, biasfluoroethylene-hexafluoropropylene-TFE copolymer and ethylene- The fluorine resins such as TFE copolymer；Glass transition temperature is 23 DEG C of fluorine-containing rubbers below in above-mentioned fluorine resin；Virtue Fragrant race's polymer；Styrene-butadiene copolymer and its hydride, methacrylate copolymer, acrlylonitrile-acrylate are total The rubbers such as polymers, copolymer in cinnamic acrylic ester, ethylene propylene rubber, polyvinyl acetate；The fusing points such as polysulfones, polyester Or the resin that glass transition temperature is 180 DEG C or more；Polyvinyl alcohol, polyethylene glycol, cellulose ether, sodium alginate, polypropylene Water-soluble polymers such as acid, polyacrylamide, polymethylacrylic acid etc..
In addition, thermoplastic resin contained by porous layer involved in an embodiment of the invention is preferably fragrant adoption Close object.Here, " aromatic polymer " refers to containing aromatic rings, that is, indicates that the monomer for constituting above-mentioned thermoplastic resin includes virtue Fragrant compounds of group.
As the concrete example of above-mentioned aromatic polymer, aromatic polyamide, aromatic polyimide, aromatic series can be enumerated Polyester, aromatic copolycarbonate, aromatic series polysulfones and aromatic polyether etc..It is preferably fragrant as above-mentioned aromatic polymer Fragrant polyamide, aromatic polyimide and aromatic polyester, more preferably aromatic polyester.In addition, aromatic polymer There is no all aromatic polymer of aliphatic carbon on main chain preferably.
In this specification, the generic name of polymer indicates main bonding pattern possessed by the polymer.For example, this Polymer contained by the thermoplastic resin of invention be referred to as the aromatic polymer of aromatic polyester when, indicate the aromatic series polymerize The above are ester bonds for 50% of main chain bond number in the molecule of object.It should be noted that the above-mentioned aromatic series for being known as aromatic polyester In polymer, other keys (for example, amido bond, imide bond etc.) other than ester bond can also be included in the key for constituting main chain.
Thermoplastic resin contained by porous layer involved in an embodiment of the invention is preferably condensation polymer.This In, " condensation polymer " indicates that the monomer as raw material is made to carry out polymer (polymer) made of polycondensation.
Thermoplastic resin contained by porous layer involved in an embodiment of the invention is usually at 25 DEG C or less Thermoplastic resin without softening point.That is, temperature ring of the porous layer involved in an embodiment of the invention at 25 DEG C It is closely sealed with electrode along with flexible deformation under border.That is, flexible deformation occurs for above-mentioned thermoplastic resin, thus porous layer with it is non-aqueous The contact area of electrolyte secondary batteries electrode increases, thus porous layer involved in an embodiment of the invention and electricity It is extremely closely sealed.
, nonaqueous electrolytic solution secondary battery related with the contact area of porous layer and nonaqueous electrolytic solution secondary battery electrode With the structure of electrode, determined according to the mass ratio of electrode active material and adhesive.
Therefore, porous layer involved in an embodiment of the invention and composition nonaqueous electrolytic solution secondary battery electrode Material (material) it is unrelated, and the nonaqueous electrolytic solution secondary battery probably fixed with the mass ratio of electrode active material and adhesive With the adaptation between electrode with fixation.
Here, " thermoplastic resin for not having softening point at 25 DEG C or less " includes the heat of the softening point with 25 DEG C or more Plastic resin and do not observe softening point, both thermoplastic resins thermally decomposed before softening.
In addition, the thermoplastic resin preferably thermoplastic resin (the heat resistance tree without softening point when being lower than 150 DEG C Rouge).
Since above-mentioned thermoplastic resin does not have softening point, thus the heat that while being worked by battery generates when being lower than 150 DEG C It is difficult to make the nonaqueous electrolytic solution secondary battery lamination spacer containing above-mentioned porous layer to soften, therefore can be improved non-aqueous solution electrolysis The heat resistance of liquid secondary battery lamination spacer.
It should be noted that thermoplastic resin contained by porous layer involved in an embodiment of the invention can be with It is a kind, or the mixture of two or more resin.
As aromatic polyamide, can enumerate the fully aromatic polyamides such as para-aramid and aromatic polyamides, Semiaromatic polyamide composition, 6T nylon, 6I nylon, 8T nylon, 10T nylon and their modifier or their copolymer Deng.
As aromatic polyimide, prepared complete preferably by the polycondensation of aromatic diacid acid anhydride and aromatic diamine Aromatic polyimide.As the concrete example of the dicarboxylic anhydride, pyromellitic acid dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetramethyls can be enumerated Acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,2 '-bis- (3,4- dicarboxyphenyi) hexafluoropropane, 3,3 ', 4, 4 '-bibenzene tetracarboxylic dianhydrides etc..As the concrete example of the diamines, oxo diphenylamines, p-phenylenediamine, benzophenone two can be enumerated Amine, 3,3 '-methylene dianiline (MDA)s, 3,3 '-diaminobenzophenones, 3,3 '-diamino diphenyl sulfones, 1,5 '-naphthylenediamines etc., this Invention is not limited to this.It in the present invention, can be suitably using the polyimides dissolved in solvent.It is sub- as this polyamides Amine, for example, the polyimides of the condensation polymer of 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic acid dianhydrides and aromatic diamine can be enumerated.
As aromatic polyester, for example, polymer as shown below can be enumerated.The preferably full fragrance of these aromatic polyesters Adoption ester.
(1) polymer for polymerizeing aromatic hydroxy-carboxylic, aromatic dicarboxylic acid and aromatic diol,
(2) polymer for polymerizeing aromatic hydroxy-carboxylic of the same race or not of the same race,
(3) polymer for polymerizeing aromatic dicarboxylic acid and aromatic diol,
(4) it polymerize aromatic hydroxy-carboxylic, aromatic dicarboxylic acid and the aromatic amine with phenolic hydroxyl group poly- Object is closed,
(5) polymer for polymerizeing aromatic dicarboxylic acid and the aromatic amine with phenolic hydroxyl group,
(6) polymer for polymerizeing aromatic hydroxy-carboxylic, aromatic dicarboxylic acid and aromatic diamine,
(7) it polymerize aromatic hydroxy-carboxylic, aromatic dicarboxylic acid, aromatic diamine and aromatic diol Polymer,
(8) make aromatic hydroxy-carboxylic, aromatic dicarboxylic acid, aromatic amine and aromatic diol with phenolic hydroxyl group It polymerize obtained polymer.
In above-mentioned Wholly aromatic polyester, from the viewpoint of dissolubility in a solvent, preferably above-mentioned (4)~(7) Or the aromatic polyester of (8).Because dissolubility in a solvent is excellent, therefore it can be improved the productivity of porous layer.
It should be noted that substituting these aromatic hydroxy-carboxylics, aromatic dicarboxylic acid, aromatic diol, aromatic series two Amine and aromatic amine with phenolic hydroxyl group, ester formative derivative or the amide formative that they also can be used are derivative Object.
Here, as the ester formative derivative of carboxylic acid or amide formative derivative, for example, can enumerate：Carboxyl becomes For the substance for promoting polyester to generate reaction or polyamide generates the high derivative of the acid chloride of reaction, acid anhydrides isoreactivity；Carboxylic Base and alcohols, glycol, amine etc. that polyester or polyamide are generated by ester exchange reaction or amide exchange reaction formed ester or The derivative etc. of person's amide.
In addition, the ester formative derivative as phenolic hydroxyl group, for example, can enumerate：To generate polyester by ester exchange reaction Mode, phenolic hydroxyl group and carboxylic acids form the ester formative derivative etc. of ester.
In addition, the amide formative derivative as amino, for example, can enumerate：It is poly- to be generated by amide exchange reaction The mode and carboxylic acids of amide form the amide formative derivative etc. of amide.
In addition, aromatic hydroxy-carboxylic, aromatic dicarboxylic acid, aromatic diol and aromatic amine with phenolic hydroxyl group, Aromatic diamine, if in the degree for not hindering ester formative or amide formative, can with the alkyl such as methyl, ethyl, Aryl such as phenyl etc. are replaced.
As the constitutional repeating unit of above-mentioned Wholly aromatic polyester, can example go out following units, but not limited to this.
From the constitutional repeating unit of aromatic hydroxy-carboxylic：
【Chemical formula 1】
Above-mentioned constitutional repeating unit can also be replaced by alkyl or aryl.
From the constitutional repeating unit of aromatic dicarboxylic acid：
【Chemical formula 2】
Above-mentioned constitutional repeating unit can also be replaced by alkyl or aryl.
From the constitutional repeating unit of aromatic diol：
【Chemical formula 3】
Above-mentioned constitutional repeating unit can also be replaced by alkyl or aryl.
From the constitutional repeating unit of the aromatic amine with phenolic hydroxyl group：
【Chemical formula 4】
Above-mentioned constitutional repeating unit can also be replaced by alkyl or aryl.In addition, be bonded to the hydrogen atom of nitrogen-atoms Part or all can also be replaced by alkyl, acyl group etc..
From the constitutional repeating unit of aromatic diamine：
【Chemical formula 5】
Above-mentioned constitutional repeating unit can also be replaced by halogen atom, alkyl or aryl.
It should be noted that as the alkyl that can replace constitutional repeating unit, usually using the alkane of such as carbon number 1~10 Base, wherein it is preferred that methyl, ethyl, propyl or butyl.As the aryl that can replace constitutional repeating unit, usually using such as carbon The aryl of number 6~20, wherein it is preferred that phenyl.In addition, part or all for being bonded to the hydrogen atom of nitrogen-atoms can also be by alkane Base, acyl group etc. replace.As the halogen atom that can replace constitutional repeating unit, for example, fluorine atom, chlorine atom, bromine can be enumerated Atom.
From the heat resistance for further increasing nonaqueous electrolytic solution lamination spacer involved in an embodiment of the invention From the perspective of, Wholly aromatic polyester preferably comprises above-mentioned (A1)、(A3)、(B1)、(B2) or (B3) repetitive unit represented by formula.
Here, as containing above-mentioned repetitive unit structural unit preferred combination, for example, can enumerate following (a)~ (d)。
(a)：
Above-mentioned constitutional repeating unit (A1)、(B2) and (D1) combination,
Above-mentioned constitutional repeating unit (A3)、(B2) and (D1) combination,
Above-mentioned constitutional repeating unit (A1)、(B1)、(B2) and (D1) combination,
Above-mentioned constitutional repeating unit (A3)、(B1)、(B2) and (D1) combination,
Above-mentioned constitutional repeating unit (A3)、(B3) and (D1) combination or
Above-mentioned constitutional repeating unit (B1)、(B2) or (B3) and (D1) combination.
(b)：In each combination of above-mentioned (a), (D1) part or all replace with (D2) obtained from combine.
(c)：In each combination of above-mentioned (a), (A1) a part replace with (A3) obtained from combine.
(d)：In each combination of above-mentioned (a), (D1) part or all replace with (C1) or (C3) obtained from combine.
(e)：In each combination of above-mentioned (a), (D1) part or all replace with (E1) or (E5) obtained from combine.
As further preferred combination, further preferably from selected from P-hydroxybenzoic acid and 2- hydroxyl -6- naphthalene 10~50 moles of % of constitutional repeating unit of at least one of formic acid compound, it derives from selected from 4- hydroxyanilines and 4, 10~50 moles of % of constitutional repeating unit of at least one of 4 '-diamino-diphenyl ethers compound, it derives from selected to benzene 10~50 moles of % of constitutional repeating unit of at least one of dioctyl phthalate and M-phthalic acid compound, from quinhydrones 10~19 moles of % of constitutional repeating unit, further, particularly preferably containing the constitutional repeating unit from 4- hydroxyanilines 10~35 moles of %, 20~45 moles of % of constitutional repeating unit from M-phthalic acid.
As the preparation method of above-mentioned thermoplastic resin, method known to those skilled in the art can be used, without spy It does not limit.An example of preparation method as above-mentioned thermoplastic resin, the preparation method of aromatic polyester out illustrated below.
As the preparation method of aromatic polyester, for example, can enumerate：By aromatic hydroxy-carboxylic or aromatic diol, tool There are the aromatic amine of phenolic hydroxyl group, aromatic diamine to be acylated (acylation reaction) with excessive fatty acid anhydride, obtain acylate, The side that the acylate made carries out transesterification with aromatic hydroxy-carboxylic and/or aromatic dicarboxylic acid, amide exchanges and polymerize Method.
In acylation reaction, the additive amount of fatty acid anhydride is preferably that 1.0~1.2 times of the summation of phenolic hydroxyl group and amino are worked as Amount.
Acylation reaction is preferably reacted 5 minutes~10 hours under the conditions of 130~180 DEG C, more preferably in 140~160 DEG C of items It is reacted 10 minutes~3 hours under part.
Fatty acid anhydride used in acylation reaction is not particularly limited, for example, can enumerate acetic anhydride, propionic andydride, butyric anhydride, Isobutyric anhydride etc. can also mix two or more use.From the viewpoint of price and operability, preferably acetic anhydride.
In the polymerization based on transesterification, amide exchange, the acyl group of acylate is preferably 0.8~1.2 times of equivalent of carboxyl. In addition, polymerization temperature is preferably carried out at 400 DEG C or less, further preferably carried out at 350 DEG C or less.
It should be noted that acylation reaction, the polymerization exchanged based on transesterification, amide can also be in the presence of a catalyst It carries out.As above-mentioned catalyst, the catalyst for being currently known the catalyst for polymerization as polyester can be used.
Based on transesterification, amide exchange polymerization usually by melt polymerization carry out, but also can be used together melt polymerization and Solid phase.About solid phase, polymer can be taken out from melt polymerization process, after solidification, is pulverized into powder Or flake, then carried out by well known method for solid phase polymerization.Specifically, for example, can enumerate：In the torpescence atmosphere such as nitrogen Under, 1~30 hour heat-treating methods etc. are carried out under 20~350 DEG C, solid state shape.After solid phase, obtained aromatic series Polyester can also be granulated and be used by known method.
< inorganic filler >
Porous layer involved in an embodiment of the invention preferably also contains inorganic filler.Above-mentioned inorganic filler is exhausted The inorganic filler of edge can be made of as its material inorganic powder.
As above-mentioned inorganic powder, for example, can enumerate：By metal oxide, metal nitride, metal carbides, metal The powder that the inorganic matters such as hydroxide, carbonate, sulfate are constituted if particular instantiation, can be enumerated：By aluminium oxide, titanium dioxide The powder of the compositions such as silicon, titanium dioxide, aluminium hydroxide or calcium carbonate.The inorganic powder can be used alone, and can also mix makes Use two or more.In these inorganic powders, chemically the point of stability considers, preferably alumina powder.Here, it more preferably constitutes The particle of inorganic filler is entirely aluminium oxide particles, and the particle of even more preferably composition inorganic filler is entirely to aoxidize aluminum shot Son, and the embodiment of part of it or all substantially spherical aluminium oxide particles.It should be noted that in the present invention In, substantially spherical aluminium oxide particles include true spheroidal particle.
The content of inorganic filler in porous layer involved in an embodiment of the invention and inorganic filler material Specific gravity is related, for example, the weight of inorganic filler is opposite in the case where the particle for constituting inorganic filler all aluminium oxide particles In the total weight of porous layer be usually 20 weight % or more and 95 weight % hereinafter, preferably 30 weight % or more and 90 weight % Below.Above range can suitably be set according to the specific gravity of inorganic filler material.
As the shape of above-mentioned inorganic filler, substantially spherical, plate, column, needle-shaped, palpus shape, threadiness etc. can be enumerated, Arbitrary particle can be used, but from the perspective of uniform hole easy to form, preferably substantially spherical particle.In addition, from From the perspective of the strength characteristics and flatness of porous layer, the average grain diameter of the particle of inorganic filler, preferably 0.01 μ are constituted M or more and 1 μm or less.Here, average grain diameter uses the value measured by scanning electron microscope photo.Specifically, from this 50 particles are arbitrarily extracted in the particle of photo photographs, measure respective partial size, use its average value.
The physical property > of < porous layer
In the following the description about the physical property of porous layer, in the case where porous layer is laminated in the two sides of porous substrate, until Refer to the object of the porous layer in the face facing with anode when nonaqueous electrolytic solution secondary battery is made, being laminated in porous substrate less Property.
As long as although considering the thickness of manufactured nonaqueous electrolytic solution secondary battery lamination spacer and suitably determining , but in the case where porous layer is laminated in the one or both sides of porous substrate, the film thickness of porous layer is preferably 0.5 μm~15 μm (every one side), more preferably 2 μm~10 μm (every one side).
From in the nonaqueous electrolytic solution secondary battery lamination spacer for having the porous layer, the broken of battery can be substantially prevented from Internal short-circuit caused by damage etc., and from the point of view of can maintaining in terms of the maintenance dose of electrolyte in porous layer, the preferably film of porous layer Thickness is 1 μm or more (single side is 0.5 μm or more).
On the other hand, from the nonaqueous electrolytic solution secondary battery lamination spacer entire area that can inhibit to have the porous layer Lithium ion plasma penetrate resistance (Japanese：Tou Over is resisted) increase, the deterioration of anode when preventing repeated charge-discharge cycles, Multiplying power property, the reduced aspect of cycle characteristics, and can be by inhibiting the increase of distance between anode and cathode non-to prevent From the point of view of the aspect of the enlargement of water electrolysis liquid secondary battery, preferably the film thickness of porous layer adds up to 30 μm or less (single sides with two sides It is 15 μm or less).
The voidage of porous layer involved in an embodiment of the invention is preferably 25%~80%, more preferably 30%~75%.The voidage of porous layer is for example calculated by the specific gravity of porous layer and volume.From obtained porous layer and contain From the perspective of having the ion permeability of nonaqueous electrolytic solution secondary battery lamination spacer of the porous layer, preferably above-mentioned gap Rate is within the above range.
The voidage of porous layer involved in an embodiment of the invention, by for example being calculated, being surveyed using following methods Fixed film thickness [μm], weight per unit area [g/m2] and real density [g/m3] find out.
(measurement of film thickness)
It is measured according to JIS specification (K 7130-1992), using the high accuracy number gauging machine of M Co., Ltd. itutoyo It is porous used in nonaqueous electrolytic solution secondary battery lamination spacer and nonaqueous electrolytic solution secondary battery lamination spacer The film thickness of substrate.By the difference of the film thickness of obtained nonaqueous electrolytic solution secondary battery lamination spacer and porous substrate, calculate non- The film thickness of water electrolysis liquid secondary battery insulating properties porous layer.
(weight per unit area)
Lamination spacer is used to cut out square that the length on one side is 8cm as sample from nonaqueous electrolytic solution secondary battery, Measure the weight W of the sample2(g).It is cut out from nonaqueous electrolytic solution secondary battery porous substrate used in lamination spacer The length on one side is the square of 8cm as sample, measures the weight W of the sample1(g).Then, according to the following formula (2), calculate non- The weight per unit area of water electrolysis liquid secondary battery insulating properties porous layer.
Formula (2)：Weight per unit area (g/m2)=(W2-W1)/(0.08×0.08)
(real density)
The porous layer of nonaqueous electrolytic solution secondary battery lamination spacer is cut into 4mm square~6mm square, 30 DEG C with It is lower carry out vacuum drying in 17 hours after, using dry type automatic densitometer (Micromeritics corporation AccuPyeII1340), Based on helium replacement method, real density is measured.
By film thickness [μm], the weight per unit area [g/m obtained as described above2] and real density [g/m3], under Formula calculates voidage.
Formula：The voidage [%] of the porous layer=[1- (weight per unit area [g/m of porous layer2])/{ (porous film thickness [μ m])×10-6× (real density [the g/m of porous layer3])}]×100
The air permeability of porous layer involved in an embodiment of the invention, from the nonaqueous electrolytic solution containing the porous layer From the perspective of the ion permeability of secondary cell lamination spacer, preferably 30 seconds/100cc~300 second/100cc is more excellent It is selected as 50 seconds/100cc~250 second/100cc.By making above-mentioned air permeability within the above range, can keep well above-mentioned more The ion permeability of aperture layer, as a result, can be improved the resistance value etc. of the nonaqueous electrolytic solution secondary battery containing the porous layer Battery behavior.
< peel strength >
Porous layer involved in an embodiment of the invention, under conditions of 25 DEG C, 30kN, 1 minute × 2 times, with With 92：2.7：5.3 quality ratios contain the nonaqueous electrolytic solution secondary battery electrode of electrode active material, conductive agent and binder Peel strength when being crimped is greater than 0N/m and 2.0N/m or less.
Think that there is following feature, that is, above-mentioned peel strength is bigger, i.e. the adaptation of electrode and porous layer is higher, then on It is more soft to state porous layer, it is more easy to be closely sealed with electrode.Therefore, in the case where above-mentioned peel strength is excessive, porous layer is excessively soft It is soft, therefore the emptying aperture structure inside porous layer is easy occlusion, air permeability reduces.It is empty moreover when porous layer is crimped with electrode In the case that pore structure is easier to occlude, therefore above-mentioned peel strength is excessive, in the nonaqueous electrolytic solution secondary battery that group installs, There is the air permeability of the porous layer and the nonaqueous electrolytic solution secondary battery lamination spacer comprising the porous layer to further decrease Risk.
Therefore, from the viewpoint of the deterioration for preventing above-mentioned air permeability, above-mentioned peel strength is preferably 1.7N/m or less.
On the other hand, in the case that above-mentioned peel strength is too small, have nonaqueous electrolytic solution secondary battery assembling when, electrode with Nonaqueous electrolytic solution secondary battery containing above-mentioned porous layer generates the risk of deviation with lamination spacer.
Therefore, from the viewpoint of inhibiting the generation of above-mentioned deviation, improving the productivity of nonaqueous electrolytic solution secondary battery, on Stating peel strength is greater than 0N/m, preferably 0.1N/m or more, more preferably 0.5N/m or more.
In addition, under room temperature (for example, 25 DEG C), drying regime, without the i.e. composable non-aqueous solution electrolysis of the operations such as heating Liquid secondary battery reduces the production cost of nonaqueous electrolytic solution secondary battery, from the perspective of the productivity for improving battery, it is also preferred that Above-mentioned peel strength is greater than 0N/m.
Porous layer with above-mentioned peel strength can be obtained by optimization in the thermoplastic resin contained by porous layer It arrives.For example, in the case where containing above-mentioned aromatic polymer as thermoplastic resin, by adjusting contained by aromatic polymer Para-orientation repetitive unit and meta position orientation repetitive unit amount ratio (molar ratio), so as to adjust polymer Flexibility controls peel strength for above range.In addition, only the thermoplastic resin contained by a kind of porous layer is unable to get When stating the peel strength of range, by mixing the other resins different from the resin properties, peel strength is adjusted to The range stated.As the example of 2 kinds of thermoplastic resin of mixing, the mixed of aromatic polyester and aromatic polyamide can be enumerated Close etc..
The measuring method > of < peel strength
Illustrate an example for the method for measuring above-mentioned peel strength based on Fig. 1, Fig. 2.Here, as described above, Fig. 1 shows show The schematic diagram of an example for the method that porous layer of the invention and electrode are crimped under conditions of 25 DEG C, 30kN, Fig. 2 are indicated The schematic diagram of the method for measurement peel strength of the invention is shown.
The component of Fig. 1 is as already explained.In Fig. 2,6 indicate fixture fixed position, and 7 indicate invisible tape (Japanese： メ Application デ ィ Application グ テ ー プ), 8 indicate fixture fixed position, and 9 indicate double faced adhesive tape, and 10 indicate glass epoxy board.It needs Illustrate, in Fig. 2, for marking the component of identical number with Fig. 1, the description thereof will be omitted.
As described above, by the way that measurement sample 3 and electrode 4 are crimped with method shown in FIG. 1, to obtain successively Nonaqueous electrolytic solution secondary battery component with electrode 4 and said determination sample 3.Then, for example, as shown in Fig. 2, with 4 side of electrode for the nonaqueous electrolytic solution secondary battery component that glass epoxy board 10 is attached to by double faced adhesive tape 9, will be stealthy Adhesive tape 7, which is attached in measurement sample 3, makes peel strength measurement sample.
Next, above-mentioned peel strength measurement sample to be set to the measurement of peel strength through fixture fixed position 6,8 Device (for example, small desk testing machine) is existed in a thickness direction with the test speed of 500mm/min using the measurement device Invisible tape 7 is removed in longitudinal direction, the size of power required for said determination sample 3 and electrode 4 are removed in measurement.With Obtained value is set as peel strength (N/m) divided by the width of measurement sample 3 by the measured value of the size of the power.Survey at this time Fixed condition is load sensor：50N, test length (length of measurement sample 3)：80mm, test width (measurement sample 3 Width)：25mm.
It should be noted that nonaqueous electrolytic solution secondary battery is usually film with lamination spacer, therefore will be above-mentioned more The case where aperture layer is crimped with electrode 4 and above-mentioned nonaqueous electrolytic solution secondary battery is pressed with lamination spacer and electrode 4 In the case where connecing the two, to the porous layer institute of above-mentioned porous layer and the above-mentioned nonaqueous electrolytic solution secondary battery lamination spacer of composition The pressure of application and be same with the adaptation of electrode 4.
Therefore, porous layer involved in an embodiment of the invention is under conditions of 25 DEG C, 30kN, 1 minute × 2 times Peel strength when being crimped with nonaqueous electrolytic solution secondary battery electrode, can also be by measuring using above-mentioned porous layer as extremely When a few outermost nonaqueous electrolytic solution secondary battery is crimped with lamination spacer with electrode under the conditions described above Peel strength measures.
The manufacturing method > of < porous layer
As the manufacturing method of porous layer involved in an embodiment of the invention, for example, can enumerate comprising following The method of process：It is dissolved in above-mentioned thermoplastic resin in solvent, and above-mentioned inorganic filler is arbitrarily made to be scattered in the solvent, Thus the process for being used to form the coating liquid of porous layer is prepared；The coating liquid is coated on substrate and is allowed to drying, is thus analysed The process of porous layer involved in an embodiment of the invention out.It should be noted that substrate can be used it is aftermentioned more Hole substrate or electrode etc..
Above-mentioned solvent (decentralized medium) as long as adverse effect will not be caused to substrate, can be equal by above-mentioned thermoplastic resin It is even and steadily dissolve, make above-mentioned inorganic filler uniformly and steadily disperse, be not particularly limited.As above-mentioned molten Agent (decentralized medium), specifically, N-Methyl pyrrolidone, n,N-dimethylacetamide, n,N-Dimethylformamide can be enumerated Deng.Above-mentioned solvent (decentralized medium) can be used only a kind, two or more can also be applied in combination.
As long as coating liquid can satisfy for obtain desired porous layer and required resin solid content (resin is dense Degree) and inorganic filler the conditions such as amount, then no matter be ok with which kind of method formation.Specifically, can enumerate：Make above-mentioned heat Plastic resin is dissolved in solution obtained by solvent (decentralized medium) method for adding, dispersing inorganic filler.Add the feelings of filler Under condition, it is, for example, possible to use Three One motor, homogenizer, media type disperser, pressure type dispersion machine etc. are known Dispersion machine is scattered in inorganic filler in solvent (decentralized medium).
Method on base material is applied as by coating liquid, blade coating method, scraper plate coating process, scraper coating can be used Coating method well known to method, gravure coating method, die coating method etc..
The removing method of solvent (decentralized medium) is usually by dry method.As drying means, can enumerate certainly It is so dry, air-supply drying, heat drying, be dried under reduced pressure, as long as however can fully remove solvent (decentralized medium), then Either which kind of method is ok.Alternatively, it is also possible to which solvent contained in coating liquid (decentralized medium) is being replaced into others It is dried after solvent.It is replaced into the method removed after other solvents as by solvent (decentralized medium), is specifically had It replaced with the low-boiling poor solvent such as water, alcohol, acetone, be allowed to the method for being precipitated and drying.
[embodiment 2：Nonaqueous electrolytic solution secondary battery lamination spacer]
The lamination spacer of nonaqueous electrolytic solution secondary battery involved in embodiments of the present invention 2 includes polyolefin porous Porous layer involved in film and embodiments of the present invention 1.Preferably non-water power involved in embodiments of the present invention 2 Sheet of the solution liquid secondary battery lamination spacer comprising polyolefin porous membrane and at least one side for being laminated in the polyolefin porous membrane Porous layer involved in the embodiment 1 of invention.
Nonaqueous electrolytic solution secondary battery lamination spacer involved in an embodiment of the invention has the present invention An embodiment involved in nonaqueous electrolytic solution secondary battery insulating properties porous layer, thus play can will with battery spy Property linkage air permeability remain good range and the excellent effect of battery production rate.
< polyolefin porous membrane >
Polyolefin porous membrane of the invention is the perforated membrane using polyolefin-based resins as principal component.In addition, above-mentioned porous Film is preferably microporous membrane.That is, above-mentioned perforated membrane has the structure of the micropore inside it with connection, with gas, liquid energy Enough from the polyolefin-based resins towards another side transmission as principal component.Above-mentioned perforated membrane can be formed by 1 layer, can also be by Multiple layers of formation.
Perforated membrane using polyolefin-based resins as principal component refers to that the ratio of polyolefin-based resins ingredient is in perforated membrane Constitute perforated membrane material entirety usual 50 volume % or more, preferably 90 volume % or more, more preferably 95 volume % with On.In polyolefin-based resins contained by polyolefin porous membrane, preferably comprising weight average molecular weight is 5 × 105~15 × 106Range High molecular weight components.Being especially and the polyolefin-based resins as perforated membrane containing weight average molecular weight is 1,000,000 or more Polyolefin-based resins, polyolefin porous membrane and the non-aqueous electrolyte secondary for having the polyolefin porous membrane and above-mentioned porous layer The intensity of battery lamination spacer entirety improves, therefore more preferably.
As polyolefin-based resins, for example, can enumerate ethylene, propylene, 1- butylene, 4-methyl-1-pentene, 1- hexene etc. The homopolymer (for example, polyethylene, polypropylene, polybutene) or copolymer for the high molecular weight being polymerized are (for example, ethylene-propylene Copolymer).Polyolefin porous membrane is the layer comprising a kind of these polyolefin-based resins, and/or comprising these polyenes of more than two kinds The layer of hydrocarbon system resin.Particularly, from the point of view of in terms of can prevent that (closing) super-high-current flows through at lower temperatures, preferably with ethylene Based on high molecular weight polyethylene-based resin.It should be noted that polyolefin porous membrane can be in the function for not damaging this layer In the range of energy, contain the ingredient other than polyolefin-based resins.
The air permeability of polyolefin porous membrane is usually calculated as 30 seconds/100cc~300 second/100cc with Ge Li value (Gurley value) Range, preferably 50 seconds/100cc~250 second/100cc range.In polyolefin porous membrane as having above-mentioned porous layer In the case where the component use of nonaqueous electrolytic solution secondary battery lamination spacer, it is laminated in the nonaqueous electrolytic solution secondary battery In terms of spacer can obtain sufficient ion permeability, preferred polyolefm perforated membrane has the air permeability of above range
Since the energy density of the film thickness more thin battery of perforated membrane is higher, preferably 20 μm hereinafter, more preferably 16 μ M is hereinafter, further preferably 11 μm or less.In addition, being preferably 4 μm or more from the viewpoint of film-strength.That is, the film of perforated membrane Preferably 4 μm or more and 20 μm or less of thickness.
Well known method can be used in the manufacturing method of perforated membrane, is not particularly limited.For example, can enumerate as Japan Patent It is as being recorded in No. 5476844 bulletin, filler is being added into thermoplastic resin after being configured to film, remove the filler Method.
Specifically, for example, in perforated membrane by below low comprising ultra-high molecular weight polyethylene and weight average molecular weight 10,000 In the case that the polyolefin resin of molecular weight polyolefins is formed, from the viewpoint of manufacturing cost, preferably by the inclusion of following institute Process (1)~(4) method shown manufactures.
(1) by 100 parts by weight of ultra-high molecular weight polyethylene, 5 weight of low-molecular-weight polyolefin below of weight average molecular weight 10,000 100 parts by weight of inorganic fillers such as part~200 parts by weight, calcium carbonate~400 parts by weight mixing obtains polyolefin resin combination The process of object,
(2) process of sheet material is shaped using polyolefine resin composition,
(3) process that inorganic filler is removed from process (2) resulting sheet material,
(4) by the process of process (3) resulting sheet material stretching.
In addition it is also possible to utilize the method recorded in above-mentioned each patent document.
In addition, commercially available product as characterized above also can be used as perforated membrane of the invention.
The manufacturing method > of < nonaqueous electrolytic solution secondary battery lamination spacer
Manufacture as nonaqueous electrolytic solution secondary battery lamination spacer involved in an embodiment of the invention Method can be enumerated in the manufacturing method of the porous layer involved in an embodiment of the invention above-mentioned and be used as substrate The method of said polyolefins perforated membrane.
The physical property > of < nonaqueous electrolytic solution secondary battery lamination spacer
The film thickness of nonaqueous electrolytic solution secondary battery lamination spacer of the invention is thinner, and the energy of battery more can be improved Metric density, therefore preferably, however if film thickness is thin, intensity will reduce, therefore there is the limit in manufacture.More than considering Item, the film thickness of nonaqueous electrolytic solution secondary battery lamination spacer involved in an embodiment of the invention is preferably 50 μm hereinafter, more preferably 25 μm hereinafter, further preferably 20 μm or less.In addition above-mentioned film thickness is preferably 5 μm or more.
The air permeability of nonaqueous electrolytic solution secondary battery lamination spacer involved in an embodiment of the invention with Ge Li value meter is preferably 300 seconds/100cc hereinafter, more preferably 30~250 seconds/100cc, further preferably 50~220 seconds/ 100cc.By with above-mentioned air permeability, the above-mentioned available sufficient ion of nonaqueous electrolytic solution secondary battery lamination spacer Permeability can be improved the battery of the nonaqueous electrolytic solution secondary battery containing the nonaqueous electrolytic solution secondary battery lamination spacer Characteristic, therefore preferably.
In the case where air permeability is more than above range, that is, in the case that Ge Li value is value lower than 30 seconds/100cc, by It is high in the voidage of above-mentioned nonaqueous electrolytic solution secondary battery lamination spacer, therefore, it is intended that stepped construction is roughening, knot Fruit is that have the intensity of the nonaqueous electrolytic solution secondary battery lamination spacer to decline, and the shape stability especially under high temperature becomes Obtain insufficient risk.
On the other hand, in the case where air permeability is less than above range, i.e., Ge Li value is the value higher than 300 seconds/100cc In the case of, above-mentioned nonaqueous electrolytic solution secondary battery lamination spacer cannot get sufficient ion permeability, non-aqueous solution electrolysis sometimes The battery behavior of liquid secondary battery reduces.
It should be noted that the stacking interval of nonaqueous electrolytic solution secondary battery involved in an embodiment of the invention Part, as needed can also be in the range for not damaging the purpose of the present invention other than said polyolefins perforated membrane and porous layer It is interior to include perforated membrane well known to adhesive layer, protective layer etc..
[embodiment 3：Nonaqueous electrolytic solution secondary battery component, embodiment 4：Nonaqueous electrolytic solution secondary battery]
Nonaqueous electrolytic solution secondary battery involved in embodiments of the present invention 3 is to configure in order anode, this hair with component Involved by the insulating properties porous layer of nonaqueous electrolytic solution secondary battery involved in bright embodiment 1 or embodiments of the present invention 2 And nonaqueous electrolytic solution secondary battery formed with lamination spacer and cathode.
Nonaqueous electrolytic solution secondary battery involved in embodiments of the present invention 4 includes involved by embodiments of the present invention 1 And nonaqueous electrolytic solution secondary battery insulating properties porous layer or embodiments of the present invention 2 involved in nonaqueous electrolytic solution two Primary cell lamination spacer.
Nonaqueous electrolytic solution secondary battery involved in an embodiment of the invention is, for example, the doping for passing through lithium, goes to mix The miscellaneous non-aqueous secondary battery to obtain electromotive force can have and stack gradually involved by anode, an embodiment of the invention And nonaqueous electrolytic solution secondary battery nonaqueous electrolytic solution secondary battery component made of insulating properties porous layer and cathode.Separately Outside, nonaqueous electrolytic solution secondary battery involved in an embodiment of the invention be, for example, by the doping of lithium, go doping come The non-aqueous secondary battery for obtaining electromotive force, can be to have and stacks gradually anode, involved by an embodiment of the invention Nonaqueous electrolytic solution secondary battery insulating properties porous layer, non-aqueous electrolyte secondary made of polyolefin porous membrane and cathode The lithium ion secondary battery of battery components has and stacks gradually anode, non-aqueous involved in an embodiment of the invention The lithium ion secondary electricity of nonaqueous electrolytic solution secondary battery component made of electrolyte secondary batteries lamination spacer and cathode Pond.It should be noted that the constituent element of the nonaqueous electrolytic solution secondary battery other than nonaqueous electrolytic solution secondary battery spacer It is not limited to the constituent element of following the description.
Nonaqueous electrolytic solution secondary battery involved in an embodiment of the invention usually has and encloses battery element Structure in housing material, the battery element are that electrolyte is impregnated with cathode and anode folder across an implementation of the invention The stacking interval of nonaqueous electrolytic solution secondary battery involved in porous layer or an embodiment of the invention involved in mode Part and opposed structural body forms.Nonaqueous electrolytic solution secondary battery is preferably non-aqueous electrolyte secondary battery, particularly preferably lithium Ion secondary battery.It should be noted that so-called doping, refers to occlusion, supports, adsorbs or be inserted into, refer to that lithium ion enters just The phenomenon that active material of extremely equal electrodes.In the case that electrode is set as sheet, thickness is usually 5~1000 μm or so.More Preferably 10~200 μm or so
Nonaqueous electrolytic solution secondary battery component involved in an embodiment of the invention and a reality of the invention Nonaqueous electrolytic solution secondary battery involved in mode is applied, has nonaqueous electrolytic solution two involved in an embodiment of the invention Between the stacking of primary cell nonaqueous electrolytic solution secondary battery involved in insulating properties porous layer or an embodiment of the invention Spacing body, therefore play and can remain good range and battery production by heat resistance and with the air permeability of battery behavior linkage The excellent effect of rate.
< anode >
As nonaqueous electrolytic solution secondary battery component and nonaqueous electrolytic solution involved in an embodiment of the invention The anode of secondary cell, as long as just not limited especially generally as the anode that the anode of nonaqueous electrolytic solution secondary battery uses Fixed, it is, for example, possible to use have to be formed with the work comprising positive active material and adhesive resin (binder) on the current collector The positive plate of the structure of property material layer.It should be noted that above-mentioned active material layer usually also includes conductive agent.
As above-mentioned positive active material, for example, the material that can adulterate, go doped lithium ion can be enumerated.As the material Material, specifically, for example, at least one kind of lithium composite xoide comprising transition metal such as V, Mn, Fe, Co and Ni can be enumerated.
In above-mentioned lithium composite xoide, from the high aspect of averaged discharge current potential, the tool such as more preferable lithium nickelate, cobalt acid lithium There is α-NaFeO2Lithium composite xoide, the lithium manganate having spinel structure (Japanese of type structure：リ チ ウ system マ Application ガ Application ス ピ ネ Le) etc. Lithium composite xoide with spinel structure.The lithium composite xoide can contain various metallic elements, further preferably For compound lithium nickelate.
In addition, with relative in Ti, Zr, Ce, Y, V, Cr, Mn, Fe, Co, Cu, Ag, Mg, Al, Ga, In and Sn extremely The sum of the molal quantity of Ni in the molal quantity and lithium nickelate of a kind of few metallic element, and make above-mentioned at least one metallic element Ratio be 0.1~20 mole of % mode, when using compound lithium nickelate containing the metallic element, due to being used under high capacity When cycle characteristics it is excellent, therefore particularly preferably.Wherein, for be 85% or more containing Al or Mn and Ni ratio, it is further excellent It is selected as 90% or more active material, has the Gao Rong of the nonaqueous electrolytic solution secondary battery of the anode containing the active material The cycle characteristics in use under amount is excellent, therefore particularly preferably.
The average grain diameter for constituting the particle of above-mentioned positive active material is preferably 1 μm or more and 20 μm hereinafter, further excellent It is selected as 5 μm or more and 10 μm or less.
As above-mentioned conductive material, such as natural graphite, artificial graphite, coke class, carbon black, pyrolysis carbons, carbon can be enumerated Carbonaceous materials such as fiber and organic high molecular compound sintered body etc..Above-mentioned conductive material can be used only a kind, can also combine Use two or more.
The ratio between content of above-mentioned positive active material and conductive material is with weight ratio meter, for example, 100：0.1~100：30, Preferably 100：0.5~100：10, further preferably 100：1~100：3.
As above-mentioned binder, such as can enumerate：Kynoar, the copolymer of vinylidene, polytetrafluoroethylene (PTFE), tetrafluoro The copolymerization of ethylene-hexafluoropropene copolymer, the copolymer of tetrafluoroethylene-perfluoroalkyl vinyl ether, ethylene-tetrafluoroethylene Object, biasfluoroethylene-hexafluoropropylene-tetrafluoroethene copolymer, thermoplastic polyimide, polyethylene, polypropylene, carboxymethyl cellulose Element or the thermoplastic resins such as its ammonium salt or alkali metal salt, hydroxyethyl cellulose.It should be noted that binder also has work For the function of thickener.
The ratio between above-mentioned positive active material and the content of binder, with weight ratio meter, for example, 100：0.1~100：10, Preferably 100：0.5~100：6.
As above-mentioned positive electrode collector, for example, the conductors such as Al, Ni and stainless steel.Wherein, due to being easily worked For film, cheap, therefore more preferable Al.
The manufacturing method of anode as sheet, for example,：By positive active material, conductive material and binder The method being press-formed on positive electrode collector；Using organic solvent appropriate by positive active material, conductive material and bonding Agent be made paste after, the muddle is spread on into positive electrode collector and pressurizes after the drying and is bonded to the method on positive electrode collector； Deng.
< cathode >
Nonaqueous electrolytic solution secondary battery component and nonaqueous electrolytic solution secondary battery as an embodiment of the invention Cathode, as long as generally as nonaqueous electrolytic solution secondary battery cathode and the cathode that uses, there is no particular limitation, for example The active material layer for having and being formed on the current collector comprising negative electrode active material and adhesive resin (binder) can be used Structure negative electrode tab.It should be noted that above-mentioned active material layer usually also contains conductive auxiliary agent.
As above-mentioned negative electrode active material, for example, can adulterate, go the material of doped lithium ion, lithium metal or Lithium alloy etc..As the material, for example, carbonaceous material etc..As carbonaceous material, natural graphite, artificial can be enumerated Graphite, coke class, carbon black and pyrolysis carbons etc..
As above-mentioned negative electrode collector, for example, Cu, Ni and stainless steel etc., especially because in lithium ion secondary It is difficult to form alloy with lithium in battery and be easily worked as film, therefore more preferable Cu.
The manufacturing method of cathode as sheet, for example,：Negative electrode active material is added on negative electrode collector Molded method；Cathode current collection is spread on after negative electrode active material is made paste using organic solvent appropriate, by the muddle Body and pressurizeed after the drying and the method that anchors at negative electrode collector；Deng.In above-mentioned paste, preferably comprises above-mentioned conduction and help Agent and above-mentioned binder.
< nonaqueous electrolytic solution >
As long as the nonaqueous electrolytic solution of nonaqueous electrolytic solution secondary battery involved in an embodiment of the invention is general Nonaqueous electrolytic solution used in nonaqueous electrolytic solution secondary battery, there is no particular limitation, can be used for example lithium salts is molten Solution in organic solvent made of nonaqueous electrolytic solution.As lithium salts, for example, LiClO4、LiPF6、LiAsF6、 LiSbF6、LiBF4、LiCF3SO3、LiN(CF3SO2)2、LiC(CF3SO2)3、Li2B10Cl10, lower aliphatic lithium carboxylate salt and LiAlCl4Deng.Above-mentioned lithium salts can be used only a kind, two or more can also be applied in combination.
As the organic solvent for constituting nonaqueous electrolytic solution, for example,：Carbonates, ethers, esters, nitrile, acyl Amine, carbamates and sulfur-containing compound and imported into these organic solvents it is fluorine-based made of fluorine-containing organic solvent Deng.Above-mentioned organic solvent can be used only a kind, two or more can also be applied in combination.
The manufacturing method > of < nonaqueous electrolytic solution secondary battery component and nonaqueous electrolytic solution secondary battery
As the manufacturing method of nonaqueous electrolytic solution secondary battery component involved in an embodiment of the invention, example It can such as enumerate：Configure in order porous layer involved in above-mentioned anode, an embodiment of the invention or of the invention one The method of the lamination spacer of nonaqueous electrolytic solution secondary battery involved in embodiment and cathode.
In addition, the manufacturing method as nonaqueous electrolytic solution secondary battery involved in an embodiment of the invention, example Such as, after forming nonaqueous electrolytic solution secondary battery component using the above method, to the shell for becoming nonaqueous electrolytic solution secondary battery The nonaqueous electrolytic solution secondary battery component is put into the container of body, then, after being full of in the container with nonaqueous electrolytic solution, It is closed while decompression, it is possible thereby to manufacture nonaqueous electrolytic solution secondary battery involved in an embodiment of the invention.
Embodiment
[measuring method]
Utilize the nonaqueous electrolytic solution secondary battery manufactured in method measurement Examples 1 to 3 as shown below, comparative example 1~2 With lamination spacer and the physics value of porous layer.
The measurement > of < film thickness
In Examples 1 to 3, comparative example 1~2, according to JIS specification (K 7130-1992), Co., Ltd. is used The high accuracy number gauging machine measurement nonaqueous electrolytic solution secondary battery lamination spacer and polyolefin porous of Mitutoyo The film thickness of film calculates the film thickness of porous layer according to formula (1).
Formula (1)：The film thickness [μm] of porous layer=(film thickness [μm] of lamination spacer)-(film thickness [μ of polyolefin porous membrane m])
The measurement > of the voidage of < porous layer
(weight per unit area)
In Examples 1 to 3, comparative example 1~2, the square that the length for cutting out one side from polyolefin porous membrane is 8cm is made For sample, the weight W of the sample is measured1(g).In addition, cutting out one side from nonaqueous electrolytic solution secondary battery with lamination spacer Length is the square of 8cm as sample, measures the weight W of the sample2(g).Then, according to the following formula (2), non-aqueous solution electrolysis is calculated The weight per unit area of liquid secondary battery insulating properties porous layer.
Formula (2)：Weight per unit area (g/m2)=(W2-W1)/(0.08×0.08)
Film thickness [μm], weight per unit area [g/m by the porous layer for being calculated, being measured by the above method2] and it is porous Real density [the g/m of layer3], according to the following formula (3), calculate the voidage of porous layer.
Formula (3)：The voidage [%] of the porous layer=[1- (weight per unit area [g/m of porous layer2])/{ (porous film thickness [μm])×10-6× (real density [the g/m of porous layer3])}]×100
The measurement > of < peel strength
The nonaqueous electrolytic solution secondary battery lamination spacer manufactured in Examples 1 to 3, comparative example 1~2,25 DEG C, 30kN, peel strength when crimped under conditions of 1 minute × 2 times with electrode (anode) surveyed with the following method It is fixed.
(positive production process)
Weigh positive active material (CellSeed C-10N (Nippon Chemical Ind's system), LiCoO2, average grain 10 μm of diameter, real density 4.8g/cm3) 92 parts by weight, conductive agent (acetylene black (Deuki Kagaku Kogyo Co., Ltd's system), real density 2.2g/cm3) 2.7 parts by weight, adhesive 1 (PTFE31-JR (three well Du Pont fluorine chemistry Co. Ltd. systems), real density 2.2g/ cm3) 4.55 parts by weight, adhesive 2 (Serogen 4H (Di-ichi Kogyo Seiyaku Co., Ltd.'s system), real density 1.4g/cm3)0.75 Parts by weight.A certain amount of water is added in kneading machine, be added above-mentioned adhesive 2 and dissolve after, be added above-mentioned positive active material, Above-mentioned conductive agent, above-mentioned adhesive 1 are simultaneously kneaded, add water be adjusted so that viscosity be 2700 ± 1000cp, obtain just Pole mixture.The anode mixture is coated on to 20 μm of thickness and the not no two sides of the aluminium foil in gap as positive electrode collector sheet material Specific part and after drying, by roll pressing be calendered to coated film with a thickness of 140 μm of (apparent density 3.5g/cm3) and obtain The anode for being 54mm to width.
(crimping process)
It regard above-mentioned anode as electrode 4, it will be between the nonaqueous electrolytic solution secondary battery that manufactured in embodiment, comparative example stacking Spacing body uses above-mentioned anode and above-mentioned nonaqueous electrolytic solution secondary battery using method as shown in Figure 1 as measurement sample 3 Lamination spacer is crimped.
Electrode 4 and measurement sample 3 are cut into the rectangle of 25mm × 80mm.Then, make the more of said determination sample 3 The face of aperture layer side is overlapped with the one side of above-mentioned electrode 4, uses desk-top pressuring machine (TESTER Industry Co., Ltd system, desk-top Test Press SA-303), above-mentioned electrode 4 and said determination are carried out with sample 3 under conditions of 25 DEG C, 30kN, 1 minute × 2 times Crimping.That is, applying power 1 minute (pressurizeing for the first time) of 30kN to electrode 4 and measurement sample 3 using desk-top pressuring machine 1a, 1b Afterwards, lotus is temporarily removed, position is and then changed, applies power 1 minute (second of pressurization) of 30kN again.As a result, obtain according to The secondary secondary cell component with above-mentioned electrode 4 and said determination sample 3.It should be noted that above-mentioned crimping is in platform Formula pressuring machine 1a and said determination sandwiched polyethylene terephthalate (PET) film 2 between sample 3, in desk-top pressuring machine Sandwiched PET film 5 between 1b and above-mentioned electrode 4 and carry out.
(mensuration operation of peel strength)
It regard above-mentioned anode as electrode 4, it will be between the nonaqueous electrolytic solution secondary battery that manufactured in embodiment, comparative example stacking Spacing body measures above-mentioned peel strength using method as shown in Figure 2 as measurement sample 3.
With double faced adhesive tape 9 (NICHIBAN Co. Ltd. system, trade name：Na イ ス タ ッ Network) by glass epoxy board 10 (Hitachi Chemical Co., Ltd.'s system, trade name：MCL-E-67 4 side of electrode for the secondary cell component) being attached to, will be stealthy Adhesive tape 7 (Japanese 3M Co. Ltd. system) is attached to 3 side of said determination sample, makes peel strength measurement sample.Next, will Above-mentioned peel strength measurement sample is set to (the Shimano Inc's production of small desk testing machine through fixture fixed position 6,8 It is made, EZ Test EZ-L), using the small desk testing machine, in a thickness direction with the test speed of 500mm/min in length Invisible tape 7 is removed on edge direction, the size of power required for said determination sample 3 and above-mentioned electrode 4 are removed in measurement. Peel strength (N/m) is set as divided by the value that the width (25mm) of measurement sample 3 obtains with the measured value of the size of the power.At this time Determination condition be load sensor：50N, test length (length of measurement sample 3)：80mm, test width (use by measurement The width of sample 3)：25mm.
The measurement > of < air permeability
Based on JIS P 8117, makees made digital timing type Ge Lishi air permeability using Toyo Co., Ltd.'s essence mechanism and survey Determine instrument, measures the ventilative of the nonaqueous electrolytic solution secondary battery lamination spacer manufactured in Examples 1 to 3, comparative example 1~2 It spends (Ge Li value).
[embodiment 1]
The synthesis > of < thermoplastic resin
Using method as shown below, Wholly aromatic polyester is synthesized as thermoplastic resin.
2- is added into the reactor for having agitating device, torquemeter, nitrogen ingress pipe, thermometer and reflux cooler Hydroxyl -6- naphthoic acid 941g (5.0 moles), 4- hydroxyl acetanil 377.9g (2.5 moles), M-phthalic acid 415.3g (2.5 moles) and acetic anhydride 867.8g (8.5 moles).Then, after fully being replaced in reactor with nitrogen, in nitrogen gas It flows down and the temperature of inside reactor is warming up to 150 DEG C with 15 minutes, kept for (150 DEG C) of the temperature flow back within 3 hours.
Thereafter, the by-product acetic acid distillated and unreacted acetic anhydride are distilled off on one side, were risen on one side with 170 minutes Temperature will confirm that the time point of the rising of torque is considered as reaction and terminates to 300 DEG C, take out content.The content is cooled to Room temperature (25 DEG C) after being crushed with pulverizer, obtains the Wholly aromatic polyester powder of lower molecular weight.
Further, by the way that the Wholly aromatic polyester powder to be carried out in 180 DEG C to heat treatment 5 hours under nitrogen atmosphere, Then heat treatment 5 hours is carried out at 250 DEG C, to carry out solid phase.
The Wholly aromatic polyester of thus obtained higher molecular weight is known as aromatic polyester A.By above-mentioned aromatic polyester A40g is added in n-methyl-2-pyrrolidone (hereinafter referred to as " NMP ") 360g, heats 2 hours at 100 DEG C, to obtain virtue 10% solution of fragrant adoption ester A.
The manufacture > of < nonaqueous electrolytic solution secondary battery lamination spacer
By 10% solution of above-mentioned aromatic polyester A, alumina particulate (sumitomo chemical company system；Trade name " AKP3000 ") and solvent (NMP) mixed so that above-mentioned aluminium oxide of the above-mentioned aromatic polyester A relative to 50 parts by weight Particle is 50 parts by weight.Then, solvent (NMP) is added in obtained mixed liquor, being adjusted to solid component concentration, (aluminium oxide is micro- The concentration of grain and aromatic polyester A) it is 6 weight %, obtain dispersion liquid.
Then, by obtained dispersion liquid homogenizer (IKA system；Trade name " T18digital ULTRA TURRAX ") It is stirred, mixes under room temperature (25 DEG C), with 10000rpm, 3 minutes conditions.Then, using high pressure dispersing machine (three Hes Engineering system；Trade name " desk-top homogenizer "), dispersed under conditions of 50MPa × 2 time, obtains coating liquid.
Knife coating is used to be coated on perforated membrane (16 μ of thickness as the polyethylene of polyolefin porous membrane obtained coating liquid M, voidage 54%) on, so that the solid component in coating liquid is every 1 square metre of 8.9g.By obtained coating i.e. laminated body It is put into the humidification baking oven of 60 DEG C of relative humidity 80% 1 minute, is cleaned with ion exchange water thereafter, then made with 80 DEG C of baking oven Drying, obtain nonaqueous electrolytic solution secondary battery lamination spacer.
[embodiment 2]
The synthesis > of < thermoplastic resin
Using method same as Example 1,10% solution of aromatic polyester A is prepared.
Then, using 5 liters of detachable flasks with stirring blade, thermometer, nitrogen ingress pipe and powder adding mouth, benefit The method shown in following carries out the synthesis of the aromatic polyamide resin as thermoplastic resin.
Detachable flask is sufficiently dry, the NMP of 4200g is added, 2 hours calcium chloride has been dried in addition at 200 DEG C 272.65g 100 DEG C are warming up to after.It after calcium chloride is completely dissolved, is restored to the temperature in the flask room temperature (25 DEG C), adds P-phenylenediamine (hreinafter referred to as PPD) 132.91g, is completely dissolved the PPD, obtains solution.It is kept in the temperature for making the solution In the state of 20 ± 2 DEG C, tere-phthaloyl dichloride (hreinafter referred to as TPC) 243.32g was divided into 10 parts every about 5 minutes The solution is added.Thereafter, in the state of making the temperature of acquired solution be maintained at 20 ± 2 DEG C, the solution is made to carry out 1 small Shi Laohua stirs 30 minutes to remove bubble under reduced pressure, obtains 6% solution of aromatic polyamide resin.
The manufacture > of < nonaqueous electrolytic solution secondary battery lamination spacer
By 10% solution of above-mentioned aromatic polyester A, 6% solution of above-mentioned aromatic polyamide resin and solvent (NMP) into Row mixing, so that above-mentioned aromatic polyamide resin is 50 parts by weight relative to the above-mentioned aromatic polyester A of 50 parts by weight.It is obtaining Mixed liquor in be added solvent (NMP), be adjusted to solid component concentration (concentration of aromatic polyester A and aromatic polyamide resin) For 6 weight %, dispersion liquid is obtained.Then, in addition to using the dispersion liquid to be coated so that the solid component in coating liquid is every 1 Square metre using method same as Example 1, to obtain nonaqueous electrolytic solution secondary battery lamination spacer other than 3.2g.
[embodiment 3]
The synthesis > of < thermoplastic resin
Using method as shown below, the Wholly aromatic polyester as thermoplastic resin is synthesized.
In addition to 4-HBA 248.6g (1.8 moles), 4- hydroxyl acetanil 468.6g are added as raw material (7.90 rub by (3.1 moles), M-phthalic acid 681.1g (4.1 moles), quinhydrones 110.1g (1.0 moles) and acetic anhydride 806.5g You) other than, using method same as Example 1, obtain Wholly aromatic polyester.Obtained Wholly aromatic polyester is known as fragrance Adoption ester B.Then, using method same as Example 1,20% solution of aromatic polyester B is obtained.
Also, method same as Example 2 is utilized, 6% solution of aromatic polyamide resin is obtained.
The manufacture > of < nonaqueous electrolytic solution secondary battery lamination spacer
(firmly by 20% solution of above-mentioned aromatic polyester B, 6% solution of above-mentioned aromatic polyamide resin, alumina particulate Friendly chemical company's system；Trade name " AKP3000 "), gaseous oxidation aluminium (Evonik corporation；Trade name " ALC ") and solvent (NMP) Mixing, makes above-mentioned 15.5 parts by weight of aromatic polyamide resin with the above-mentioned aromatic polyester B relative to 9.5 parts by weight, makes Alumina particulate is stated to be 37.5 parts by weight, make above-mentioned 37.5 parts by weight of gaseous oxidation aluminium.Then, add in obtained mixed liquor Enter solvent (NMP), is adjusted to solid component concentration (aromatic polyester B, aromatic polyamide resin, alumina particulate and gas phase oxygen Change the concentration of aluminium) it is 10 weight %, obtain dispersion liquid.Then, it in addition to using the dispersion liquid, is coated on using knife coating as poly- The perforated membrane (11 μm of thickness, voidage 44%) of the polyethylene of alkene perforated membrane is so that the solid component in coating liquid is every 1 flat Other than square rice 2.0g, using method same as Example 1, nonaqueous electrolytic solution secondary battery lamination spacer is obtained.
[comparative example 1]
The manufacture > of < nonaqueous electrolytic solution secondary battery lamination spacer
In alumina particulate (sumitomo chemical company system；Trade name " AKP3000 ") 100 mass parts, carboxymethyl cellulose be (big Match fine jade fine chemistry industry system, article number 1110) 3 mass parts mixture in add water so that solid component be 29 weight %, obtain Mixture.Use rotation/revolution mixing machine " あ わ と り Practice Taro " (Co., Ltd.'s THINKY system；Registered trademark), to what is obtained 2 stirrings, mixing are carried out under conditions of mixture is under room temperature (25 DEG C), 2000rpm, 30 seconds, obtain stirring mixture.? To stirring mixture in be added 14 mass parts of isopropanol, become solid component be 28 weight % uniform slurry, applied Apply liquid.Obtained coating liquid is coated on using knife coating the polyethylene as polyolefin porous membrane perforated membrane (16 μm of thickness, Voidage 54%) on, so that the solid component in coating liquid is every 1 square metre of 6.0g.Obtained coating i.e. laminated body is existed It is 5 minutes dry at 65 DEG C, obtain nonaqueous electrolytic solution secondary battery lamination spacer.
[comparative example 2]
The synthesis > of < aromatic polyamide resin
Into 5 liters of (l) detachable flasks with stirring blade, thermometer, nitrogen ingress pipe and powder adding mouth, it is added M-phenylene diamine (MPD) 222g and NMP 3300g, is stirred and makes it dissolve.Then, 70 DEG C be will warm up and be allowed to the isophthalic two dissolved Formyl chloride 419g is added dropwise after being dissolved in NMP1000g, is reacted 60 minutes at 23 DEG C, is obtained 10% aromatic polyamide resin Solution.Obtained aromatic polyamide resin solution is dried under reduced pressure, aromatic polyamide resin solid is obtained.
The manufacture > of < nonaqueous electrolytic solution secondary battery lamination spacer
By above-mentioned aromatic polyamide resin solid, alumina particulate (sumitomo chemical company system；Trade name " AKP3000 "), With solvent (by make tripropylene glycol relative to 40 parts by weight of dimethyl acetamide of 60 parts by weight in a manner of the mixing that mixes Solvent) mixing, so that above-mentioned aromatic polyamide resin is 30 parts by weight relative to the above-mentioned alumina particulate of 70 parts by weight, so Afterwards, above-mentioned solvent is added in obtained mixed liquor, is adjusted to solid component concentration (alumina particulate+aromatic polyamide resin) For 20 weight %, dispersion liquid is obtained.Then, it other than using the dispersion liquid, using method same as Example 1, obtains Coating liquid.
Obtained coating liquid is coated on using knife coating to the perforated membrane (thickness 16 of the polyethylene as polyolefin porous membrane μm, voidage 54%) on, so that the solid component in coating liquid is every 1 square metre of 9.0g.By obtained coating i.e. laminated body At 40 DEG C, it is put into water：Dimethyl acetamide：Tripropylene glycol=50：30：1 minute in 20 coagulating basin, ion exchange is used thereafter Water cleaning, is then allowed to drying with 80 DEG C of baking oven, obtains nonaqueous electrolytic solution secondary battery lamination spacer.
[conclusion]
By the physics value of the nonaqueous electrolytic solution secondary battery lamination spacer manufactured in Examples 1 to 3, comparative example 1~2 It is shown in the following table 1.
Table 1
By the record of table 1 it is found that above-mentioned peel strength is greater than manufacturing in 0N/m and 2.0N/m Examples 1 to 3 below Nonaqueous electrolytic solution secondary battery lamination spacer air permeability, better than comparative example of the above-mentioned peel strength outside above range The air permeability of the nonaqueous electrolytic solution secondary battery lamination spacer manufactured in 1~2, can be improved battery behavior.
Even if also, knowing the nonaqueous electrolytic solution secondary battery lamination spacer manufactured in Examples 1 to 3 in room temperature Also good with the adaptation of electrode under (25 DEG C), drying regime, battery production rate is excellent.
As shown in the above, the battery of the nonaqueous electrolytic solution secondary battery lamination spacer manufactured in Examples 1 to 3 Productivity is excellent, and can be improved battery behavior.
Industrial availability
The battery of the insulating properties porous layer of nonaqueous electrolytic solution secondary battery involved in an embodiment of the invention is raw Yield is excellent, and can be improved battery behavior (resistance).Therefore, nonaqueous electrolytic solution involved in an embodiment of the invention The component that secondary cell uses insulating properties porous layer as nonaqueous electrolytic solution secondary battery is useful.
The explanation of appended drawing reference
The desk-top pressuring machine of 1a
The desk-top pressuring machine of 1b
2 polyethylene terephthalates (PET) film
3 measurement samples
4 electrodes
5 polyethylene terephthalates (PET) film
6 fixture fixed positions
7 invisible tapes
8 fixture fixed positions
9 double faced adhesive tapes
10 glass epoxy boards

Claims (5)

1. a kind of nonaqueous electrolytic solution secondary battery insulating properties porous layer is used to cover composition nonaqueous electrolytic solution secondary battery and uses The entire surface of at least one side of the porous substrate of lamination spacer, wherein
The nonaqueous electrolytic solution secondary battery insulating properties porous layer contains thermoplastic resin,
Voidage be 25% or more and 80% hereinafter,
Under conditions of 25 DEG C, 30kN, 1 minute × 2 times, and with 92：2.7：5.3 quality ratio contain electrode active material, The peel strength when nonaqueous electrolytic solution secondary battery of conductive agent and binder is crimped with electrode is greater than 0N/m and 2.0N/ M or less.
2. nonaqueous electrolytic solution secondary battery as described in claim 1 insulating properties porous layer, wherein the peel strength is 0.5N/m or more and 2.0N/m or less.
3. a kind of nonaqueous electrolytic solution secondary battery lamination spacer has nonaqueous electrolytic solution two of any of claims 1 or 2 Primary cell insulating properties porous layer and polyolefin porous membrane.
4. a kind of nonaqueous electrolytic solution secondary battery component, to configure in order anode, non-water power of any of claims 1 or 2 Solve liquid secondary battery insulating properties porous layer or nonaqueous electrolytic solution secondary battery lamination spacer as claimed in claim 3, with And cathode forms.
5. a kind of nonaqueous electrolytic solution secondary battery has nonaqueous electrolytic solution secondary battery insulation of any of claims 1 or 2 Property porous layer or nonaqueous electrolytic solution secondary battery lamination spacer as claimed in claim 3.
CN201710333820.6A 2017-05-12 2017-05-12 Nonaqueous electrolytic solution secondary battery insulating properties porous layer Pending CN108878742A (en)

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CN104508898A (en) * 2012-07-18 2015-04-08 住友化学株式会社 Adhesive layer, layer and composition
WO2015173623A1 (en) * 2014-05-14 2015-11-19 Toyota Jidosha Kabushiki Kaisha Method of manufacturing secondary battery
JP2016072197A (en) * 2014-10-02 2016-05-09 旭化成イーマテリアルズ株式会社 Separator for power storage device, and electrochemical element
CN106163806A (en) * 2014-08-29 2016-11-23 住友化学株式会社 Duplexer, distance piece and non-aqueous secondary batteries
CN106463675A (en) * 2014-06-27 2017-02-22 日本瑞翁株式会社 Composition for nonaqueous secondary cell functional layer, functional layer for nonaqueous secondary cell, and nonaqueous secondary cell

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103781861A (en) * 2011-08-31 2014-05-07 住友化学株式会社 Coating liquid, laminated porous film, and method for producing laminated porous film
CN103890998A (en) * 2011-10-21 2014-06-25 帝人株式会社 Nonaqueous secondary battery separator and non-aqueous secondary battery
CN104508898A (en) * 2012-07-18 2015-04-08 住友化学株式会社 Adhesive layer, layer and composition
WO2015173623A1 (en) * 2014-05-14 2015-11-19 Toyota Jidosha Kabushiki Kaisha Method of manufacturing secondary battery
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Application publication date: 20181123