CN106133947A - Laminated porous film and manufacture method thereof - Google Patents

Laminated porous film and manufacture method thereof Download PDF

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Publication number
CN106133947A
CN106133947A CN201580016831.0A CN201580016831A CN106133947A CN 106133947 A CN106133947 A CN 106133947A CN 201580016831 A CN201580016831 A CN 201580016831A CN 106133947 A CN106133947 A CN 106133947A
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China
Prior art keywords
layer
solvent
porous film
laminated porous
film
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Inventor
柴田健太
藤冈直史
山田宗纪
繁田朗
细田雅弘
越后良彰
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Unitika Ltd
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Unitika Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention provides a kind of when using as secondary lithium batteries separator, without compromising on the laminated porous film of the thermostability of battery behavior.The present invention relates to a kind of laminated porous film, it is characterized in that, it it is the laminated porous film being formed with the porous layer being made up of imide series macromolecule at the single or double of the porous layer being made up of polyolefin, there is following characteristic: 1) air permeability in terms of the Gurley value obtained based on JIS standard P8117, be 10 seconds/100cc～1000 seconds/100cc；2) at the porous layer being made up of imide series macromolecule non-residual alcohol series solvent；3) thickness of the porous layer being made up of imide series macromolecule is 1 μm～20 μm.

Description

Laminated porous film and manufacture method thereof
Technical field
The present invention relates to laminated porous film and manufacture method thereof.This laminated porous film such as can be suitable as lithium secondary electricity Pond separators etc., the separator of charge storage element use.
Background technology
Lithium secondary battery uses as in the electronic equipments such as electric motor car, personal computer, mobile phone because energy density is high Battery be widely used.
In the case of this lithium secondary battery produces internal short-circuit or external short circuit damaged grade the because of battery, sometimes flow through Big electric current and abnormal heating.Therefore, for lithium secondary battery, it is important that prevent certain above heating, it is ensured that high peace Quan Xing.As guaranteeing the means of this safety, when abnormal heating, separator is made to have passing through of ion between barrier electrode, Prevent the method for cutting function of heating by the most practical.
As having the separator of this cutting function, such as, use the perforated membrane being made up of polyolefin.By this perforated membrane structure The separator become is when battery abnormal heating, because polyolefin melts and atresia at 110～160 DEG C, it is possible to cut off Passing through of ion.But, because this polyolefin separator shrinks when becoming high temperature, ruptures, so in this case, Likely positive pole directly contacts with negative pole and is short-circuited, and sometimes cannot suppress the abnormal heating produced by short circuit.
As the method solving such problem, it is proposed that by the one side at the above-mentioned porous membrane layer being made up of polyolefin Or the porous layer that two-sided (following, to be sometimes abbreviated as " surface ") stacking is made up of fluorine resins such as Kynoar is to guarantee high temperature Under the method for shape stability.This stacking separator is low because of the thermostability of the fluorine resin constituting refractory layer itself, so Because of contraction during high temperature causes shape stability may not fully (such as, patent documentation 1,2).Therefore, it is proposed to above-mentioned by gathering The porous layer that on the porous membrane layer that alkene is constituted, stacking is made up of the heat-resistant resin such as polyimides, aromatic polyamides is to guarantee height The method of the shape stability under Wen.
As the method forming heat-resisting porous layer, it is proposed that will be containing heat-resistant resin (such as aromatic polyamide resin) It is coated in by gathering with good solvent (such as amide series solvent), the solution of poor solvent (such as alcohol series solvent) of this heat-resistant resin Behind the surface of the porous membrane layer that alkene is constituted, it is immersed in by the poor solvent of above-mentioned heat-resistant resin that (such as, alcohol system is molten Agent, water) in the coagulating bath that formed, cause the method (such as, patent documentation 3～6) being separated and realizing porous.
But, for the laminated porous film obtained by method as above, the alcohol system sometimes contained in heat-resistant resin Solvent, the alcohol series solvent minimal residue used when causing separated are in the heat-resisting porous layer formed.The hydroxyl of alcohol series solvent Proton is chemically active.Therefore, when using such perforated membrane as above-mentioned lithium secondary battery separator etc., residual micro- The alcohol series solvent likely dissolution in the electrolyte of lithium secondary battery of amount, with the LiPF used usually used as electrolyte6So Fluorophosphate, LiBF4Such borofluoride, LiAsF6Such fluorine arsenates etc. react.If that is, these electrolyte with The alcohol series solvent reaction of active proton, then decompose and produce fluohydric acid gas, it is therefore possible to infringement battery behavior (such as, patent Document 7,8 and quote document).It addition, in manufacture method as above, big volume production from the coagulating bath for being separated Raw containing good solvent and the waste liquid of poor solvent, therefore have problems from the viewpoint of environmental suitability.
Prior art literature
Patent documentation
Patent documentation 1: No. 4127989 publications of Japanese Patent No.
Patent documentation 2: No. 4588286 publications of Japanese Patent No.
Patent documentation 3: Japanese Unexamined Patent Publication 2002-355938 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-209570 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2006-32246 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2010-50024 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2002-75440 publication
Patent documentation 8: Japanese Unexamined Patent Publication 2005-243458 publication
Summary of the invention
Therefore, the problem of the present invention is when offer uses as secondary lithium batteries separator, special without compromising on battery The laminated porous film of the thermostability of property.Further provide for the manufacture method of the good laminated porous film of environmental suitability.
The present inventor etc. conduct in-depth research to solve above-mentioned problem, found that by being formed in by polyolefin structure The surface of the porous layer become is formed with the stacked film energy of the porous layer being made up of imide series macromolecule becoming specific composition Enough solve above-mentioned problem, thus complete the present invention.
That is, the present invention using the description below as purport.
＜ 1 ＞ laminated porous film, it is characterised in that be formed on the surface of the porous layer being made up of polyolefin by The laminated porous film of porous layer that imide series macromolecule is constituted, has a following characteristic:
1) air permeability is in terms of the Gurley value obtained based on JIS standard P8117, be 10 seconds/100cc～1000 seconds/ 100cc；
2) at the porous layer being made up of imide series macromolecule non-residual alcohol series solvent；
3) thickness of the porous layer being made up of imide series macromolecule is below 1 μm～20 μm.
＜ 2 ＞ secondary lithium batteries separator, is to use the laminated porous film described in ＜ 1 ＞.
The manufacture method of the laminated porous film described in ＜ 3 ＞ ＜ 1 ＞, it is characterised in that be made up of polyolefin The painting that the surface coating of porous layer is made up of imide series macromolecule and the mixed solvent containing amide series solvent and ether series solvent Cloth liquid and after forming film, add the solvent in the above-mentioned film of heat extraction, thus cause in film and be separated and form porous layer, Thus by the porous layer being made up of polyolefin and the porous layer stacking integration being made up of imide series macromolecule.
Because the surface stacking at the porous layer being made up of polyolefin is made up of the imide series macromolecule of excellent heat resistance The good air permeability of laminated porous film of the present invention of porous layer, and at the porous layer being made up of imide series macromolecule Non-residual alcohol series solvent, so film can be suitable as secondary lithium batteries separator.
It addition, use the manufacture method of the present invention, it is possible to obtain stacking with the simple operations utilizing heating to remove solvent many Pore membrane.
Detailed description of the invention
Hereinafter, the present invention is described in detail.
The laminated porous film of the present invention is to be formed by imide series high score on the surface of the porous layer being made up of polyolefin The laminated porous film of the porous layer that son is constituted.This laminated porous film such as can obtain as follows: by being made up of polyolefin The surface coating of porous layer (following, to be sometimes abbreviated as " S layer ") forms film containing the high molecular coating fluid of imide series, this After, add the solvent in the above-mentioned film of heat extraction, the porous layer being made up of imide series macromolecule ((below, is abbreviated as " P sometimes Layer ") integrated with S layer stackup.
S layer is the structure with the pore therein with connection, and gas, liquid can penetrate into another from a face Individual face, the perforated membrane being made up of polyolefin, become the base material of the laminated porous film of the present invention.
The ratio of the polyolefin component in S layer is preferably 90 more than volume %, more preferably 95 more than volume %.As poly- Alkene, such as, can enumerate homopolymer obtained by the olefinic polymerizations such as ethylene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene Or copolymer.Wherein, preferably by polyethylene obtained by ethylene homo, the more preferably high molecular of weight average molecular weight more than 1,000,000 Polyethylene.It addition, it is also preferred that using polypropylene obtained by propylene homo as polyolefin.
The air permeability of S layer in terms of Gurley value (JIS standard P8117), preferably 10 seconds/100cc～500 seconds/100cc, More preferably 100 seconds/100cc～300 seconds/100cc.By so setting the air permeability of S layer, it is possible to guarantee when stacking P layer As the preferable breathability of secondary lithium batteries separator.From the maintenance dose of raising electrolyte, guarantee the sight of cutting function simultaneously Point considers, the porosity of S layer preferably 20～80 volume %, more preferably 30～75 volume %.
Obtain enough breathability from when using laminated porous film as secondary lithium batteries separator, and prevent particle From the viewpoint of positive pole, negative pole are mixed into, below the μm of the aperture of S layer preferably 3, below more preferably 1 μm.Guarantee absolutely from utilizing cut-out From the viewpoint of edge, the thickness of S layer preferably 8～50 μm, more preferably 10～30 μm.Here, the thickness of S layer is as above-mentioned layer The thickness of the S layer of the material of folded perforated membrane, is the thickness measured according to JIS standard (K7130-1992).
For S layer, as long as polyolefin is main constituent, just it is not particularly limited, can be only by 1 layer of monolayer constituted Structure, it is also possible to be the multiple structure being made up of the layer of more than 2 layers.As multiple structure, such as, can enumerate by certain polyene At least one surface layer of the polyolefin layer that hydrocarbon is constituted is laminated with the structure etc. of the polyolefin layer being made up of other polyolefin.Wherein, excellent The structure being selected in the two-sided polypropylene layer being laminated with polypropylene as main constituent of the polyethylene layer with polyethylene as main constituent is (poly- Propylene layer/polyethylene layer/polypropylene layer).
The above-mentioned perforated membrane being made up of polyolefin that S layer is used can utilize commercially available product.As commercially available product, can illustrate SK company, the polyethylene perforated membrane of Celgard company, the polypropylene perforated membrane etc. of Celgard company.These commercially available porous Film be thickness be 9～25 μm and the perforated membrane with cutting function.
The imide series macromolecule of formation P layer refers to macromolecule or its precursor at main chain with imide bond.As Main chain has the high molecular typical example of imide bond, can enumerate polyimides, polyamidoimide, polyesterimide etc., but It is not limited to these.
Among above-mentioned imide series macromolecule, for example, it is possible to be preferably used polyimides or polyamidoimide and it Mixture.Here, as polyimides, it may be preferred to (polyamides dissolving in solvent is sub-to use soluble polyimide Amine).Among these imide series macromolecules, preferably mechanical characteristic, the aromatic polyimide of excellent heat resistance and aromatic series Polyamidoimide.Above-mentioned aromatic polyimide and aromatic polyamide acid imide can be thermoplastic, it is also possible to right and wrong Thermoplastic.The high molecular glass transition temperature of these imide series is preferably more than 200 DEG C, more preferably more than 220 DEG C. It is possible to guarantee the good thermostability of laminated porous film.Here, glass transition temperature (Tg) can utilize DSC (differential Heat is analyzed) confirm.
In order to manufacture the laminated porous film of the present invention, such as, can manufacture by the following method.That is, in the solvent system of use When making imide series macromolecular solution, use by dissolving imide series high molecular amide series solvent (good solvent) and insoluble acyl The mixed solvent that imines system high molecular ether series solvent (poor solvent) is constituted.Here, good solvent refers at 25 DEG C acid imide It it is the macromolecule solvent that shows the dissolubility of more than 1 mass %.It addition, poor solvent refers to dissolving high molecular to imide series Degree is less than the solvent of 1 mass %.The high molecular solution of imide series will be dissolved with in this mixed solvent (below, be sometimes abbreviated For " imide series coating fluid ") coat the surface of S layer, it is dried, it is possible to be readily derived laminated porous film.
The mixed solvent of imide series coating fluid, can be molten containing other in the range of the effect not damaging the present invention Agent.
By using such mixed solvent, it is possible to obtain not containing the film of alcohol series solvent, therefore this film is being done The dry porous layer obtained not residual alcohol series solvent.
By this imide series coating solution in the surface of S layer, hereafter, during solvent in adding heat extraction film, because of altogether The effect of the ether series solvent (poor solvent) being stored in film and cause separated, in film, form pore, therefore, it is possible to To P layer perforated membrane of stacking integration on S layer.Here, as adding the temperature of heat extraction solvent, preferably 100～150 DEG C. When dry, preferably carry out in the nitrogen or air draught of non-humidified state.It is possible to prevent moisture being mixed into film. Should illustrate, because ether series solvent does not contains chemically active proton, even if so ether series solvent minimal residue is in dried In film the most no problem.
As above-mentioned amide series solvent, such as, can enumerate METHYLPYRROLIDONE (NMP boiling point: 202 DEG C), N, N-bis- Methylformamide (boiling point: 153 DEG C), DMAC N,N' dimethyl acetamide (DMAc boiling point: 166 DEG C).They can be used alone, it is possible to To combine two or more use.Wherein, preferably NMP, DMAc.
As the use level of amide series solvent, from the viewpoint of dissolving imide series macromolecule, relative to total solvent amount It is more than 10 mass %, particularly preferably 10～70 mass %, more preferably 20～40 mass %.
Above-mentioned ether series solvent is preferably used the ether series solvent that boiling point is higher than above-mentioned amide series solvent, its boiling-point difference preferably 5 DEG C Above, more preferably more than 20 DEG C, further preferred more than 50 DEG C.Specifically, can enumerate diethylene glycol dimethyl ether (boiling point: 162 DEG C), TRIGLYME (TRGM boiling point: 216 DEG C), tetraethyleneglycol dimethyl ether (TEGM boiling point: 275 DEG C) etc..They can To be used alone, it is also possible to combine two or more and use.Wherein, particularly preferred TEGM, TRGM.
As the use level of ether series solvent, from the viewpoint of air permeability, it is more than 30 mass % relative to total solvent amount, Particularly preferably 30～90 mass %, more preferably 60～80 mass %.
Imide series coating fluid such as can utilize and be formed with commercially available U as Porous by Unitika Co., Ltd. Polyimide coating liquid and the U imide varnish such as imide varnish SP (Porous formation polyimide varnish) The polyamidoimide coating fluids such as IP (Porous is formed and uses polyamidoimide varnish).
Polyimide coating liquid can use commercially available product as above, it is possible to use by soluble polyimide powder body Being dissolved in solution obtained by above-mentioned mixed solvent, this soluble polyimide powder body is using the tetracarboxylic dianhydride's composition as raw material Coordinate with substantially equimolar with diamine component, carry out polyreaction and obtain.This polyreaction will be by making tetracarboxylic dianhydride Polyamic acid (polyimide precursor) solution that composition and diamine component reaction obtain heats and carries out.Now, preferably using as The water of by-product when being generated polyimides by polyamic acid is such as removed by azeotropic etc. and carries out.Remove water while entering The detailed content of the polymerization of the polyimides of row imidization reaction is such as referred to No. 3422061 explanations of United States Patent (USP) Book, Japanese Laid-Open Patent Publication 58-49726 publication etc..
Tetracarboxylic dianhydride's composition preferably has aromatic tetracarboxylic acid's dianhydride of aromatic rings.Become as aromatic tetracarboxylic acid's dianhydride Point, such as can use Pyromellitic Acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid (BPDA), 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, 3,3 ', 4,4 '-diphenylsulfone acid, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid (ODPA), 2,3,3,4-benzophenone tetrabasic carboxylic acid, 2, 3,6,7-naphthalene tetracarboxylic acid, 1,4,5,7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 3,3 ', 4,4 '-diphenyl-methane tetrabasic carboxylic acid, 2, Double (3,4-dicarboxyphenyi) HFC-236fa of double (3,4-dicarboxyphenyi) propane of 2-, 2,2-, 3,4,9,10-tetrabasic carboxylic acid, 2, Double [4-(3,4-di carboxyl phenyloxy) phenyl] propane of 2-, double [4-(3,4-di carboxyl phenyloxy) phenyl] HFC-236fa of 2,2-etc. Dianhydride.They can be used alone, it is also possible to combines two or more and uses.Wherein, preferably BPDA, ODPA.
The diamine component of polyimides preferably has the aromatic diamine of aromatic rings.Aromatic diamine as polyimides Composition, such as can use p-phenylenediamine, m-diaminobenzene. (MPD), 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether (DADE), 4,4 '-MDA, 3,3 '-dimethyl-4,4 '-MDA, double [4-(the 4-aminobenzene of 2,2- Epoxide) phenyl] propane (BAPP), 1,2-dianil base ethane, DADPS, diaminobenzene formailide, diaminobenzene Double (p-aminophenyl) propane of formic acid, diaminodiphenyl sulfide, 2,2-, 2,2-double (p-aminophenyl) HFC-236fa, 1,5-bis- The borontrifluoride benzene of amino naphthalenes, diaminotoluene, diaminourea, 1,4-double (p-aminophenyl epoxide) benzene, 4,4 '-bis-(p-aminophenyl epoxides) Biphenyl, diamino-anthraquinone, 4,4 '-bis-(3-aminophenoxy phenyl) sulfobenzide .s, 1,3-dianil base HFC-236fa, 1,4-are double Anilino-Octafluorobutane., 1,5-dianil base Decafluoropentane, 1,7-dianil base ten tetrafluoro heptane.They can be used alone, Can also be combined two or more use.Wherein, preferably DADE, BAPP.
As the solid component concentration of the polyimides in polyimide coating liquid, preferably 1～50 mass %, more preferably 5 ～25 mass %.
The polyimides contained in polyimide coating liquid can be polyamides obtained by polyamic acid partly imidizate Imines.Viscosity preferably 1～150Pa s, more preferably 10～100Pa s during 30 DEG C of polyimide coating liquid.
In this specification, aromatic tetracarboxylic acid two anhydride component as above and aromatic diamine composition will be made to be polymerized The polyimides of reaction is referred to as " aromatic polyimide ".
As polyamidoimide coating fluid, it is possible to use commercially available product as above, it is possible to use following solution, That is, using as the tricarboxylic acids composition (various tricarboxylic acids or its anhydride, chloride derivative) of raw material and diamine component (various diamidogen or Its di-isocyanate derivatives) coordinate with substantially equimolar, carry out polyreaction and obtain polyamidoimide powder body, will This polyamidoimide powder body is dissolved in solution obtained by above-mentioned mixed solvent.As the polymerization of polyamidoimide, can Using use by tricarboxylic acid anhydride and diisocyanate as the Carbimide. ester process of raw material, by tricarboxylic acid anhydride acyl chlorides and diamidogen as raw material Chloride method, the polyamidoimide powder body high in order to obtain the degree of polymerization, chloride method is preferably used.The detailed content of polymerization Can refer to Japanese Patent Publication 50-33120 publication (Carbimide. ester process), Japanese Patent Publication 42-15637 publication (chloride method) Deng.
Tricarboxylic acids composition preferably has the aromatic tricarboxylic acids of aromatic rings.As aromatic tricarboxylic acids composition, can enumerate partially Benzene three acyl chlorides (TMC), trimellitic anhydride (TMA), even benzene three acyl chlorides, benzene-1,2,3-tricarboxylic acid acid anhydride.Wherein preferred TMC, TMA.Furthermore it is possible to The tetrabasic carboxylic acids such as the part Pyromellitic Acid of aromatic tricarboxylic acids composition, benzophenone tetrabasic carboxylic acid or biphenyltetracarboxyacid acid are become Divide and replace.
The diamine component of polyamidoimide preferably has the aromatic diamine of aromatic rings.Virtue as polyamidoimide Fragrant race diamine component, it is, for example possible to use m-diaminobenzene. (MPD), p-phenylenediamine, 4,4 '-diphenylmethane diamine, 4,4 '-diamino Yl diphenyl ether (DADE), sulfobenzide .-4,4 '-diamidogen, diphenyl-4,4 '-diamidogen, o-tolidine, 2,4-toluenediamine, 2, 6-toluenediamine, benzene dimethylamine, naphthylenediamine or their di-isocyanate derivatives.They can be used alone, it is also possible to group Close two or more to use.Wherein, preferably DADE, MPD.
The solid component concentration of the polyamidoimide in polyamidoimide coating fluid preferably 1～50 mass %, more excellent Select 10～30 mass %.
Viscosity preferably 1～150Pa s, more preferably 5～100Pa s during 30 DEG C of polyamidoimide coating fluid.
In this specification, aromatic tricarboxylic acids composition as above and aromatic diamine composition will be made to carry out polyreaction Polyamidoimide be referred to as " aromatic polyamide acid imide ".
Various surfactant, organo silane coupling agent can be added as needed on such in imide series coating fluid Known additive.It addition, as required, can add beyond imide series macromolecule in above-mentioned imide series coating fluid Other polymer.
When the surface of S layer coating imide series coating fluid forms film, the side of the coating continuously of volume to volume can be used Method, any means in the method being coated with in the way of sheet.As the apparatus for coating now used, such as, can use die coating Machine, multilamellar die coating machine, gravure coater, comma coating machine, reverse roll coating machine, knife type coater, rod coating machine etc..As above institute State, by the solvent in the film obtained is added heat extraction, it is possible to form the P layer integrated with S layer stackup.Here, coated face Can be the one side of S layer, it is also possible to two-sided for S layer.
The air permeability of the laminated porous film of the present invention in terms of Gurley value (JIS standard P8117), be 10 seconds/100cc～ 1000 seconds/100cc, preferably 100 seconds/100cc～600 seconds/100cc, more preferably 100 seconds/100cc～500 seconds/ 100cc.By so setting air permeability, it is possible to be preferably used as secondary lithium batteries separator.That is, if Gurley value is less than 10 Second/100ml, then due to the lithium metal etc. separated out at negative pole in lithium rechargeable battery, be short-circuited with positive pole sometimes.Another Aspect, if Gurley value was more than 1000 seconds/100ml, then the internal resistance of battery uprises, and sometimes can not get high output close Degree.
For the laminated porous film of the present invention, at P layer non-residual alcohol series solvent.Here, " non-residual alcohol series solvent " represents The most non-residual alcohol series solvent, as long as do not damage the scope of the effect of the present invention, then alcohol series solvent can be with minimal residue.Alcohol Series solvent refers to methanol, ethanol, propanol, isopropanol, n-butyl alcohol, ethylene glycol, tripropylene glycol, glycerol etc..
In the porous stacked film of the present invention, the thickness of P layer is 1 μm～20 μm, below more preferably 1.5 μm～15 μm, More preferably 2 μm～10 μm.It is possible to guarantee the good breathability of P layer, and guarantee to be laminated with the perforated membrane of P layer Thermostability.If the thickness of P layer is the thinnest, then cannot guarantee the thermostability of perforated membrane.On the other hand, if the thickness mistake of P layer Thickness, then cannot guarantee breathability.Here, the thickness of P layer is that the thickness from laminated porous film deducts the thickness of above-mentioned S layer and calculates Thickness, the thickness of laminated porous film is the thickness measured according to JIS standard (K7130-1992).
The porosity of P layer is preferably 30～90 volume %, more preferably 40～80 volume %.By so setting pore Rate, it is possible to make the laminated porous film with better mechanical characteristic and breathability.Here, the adjustment of the porosity can be passed through The use level of above-mentioned ether series solvent, solvent removing condition etc. is selected to carry out.Should illustrate, the porosity of P layer is by the table of P layer See density and constitute the value that the high molecular true density of the imide series (proportion) of P layer calculates.Specifically, apparent close when P layer Degree is A (g/cm3), the high molecular true density of imide series be B (g/cm3) time, following formula calculate the porosity (volume %).
The porosity (volume %)=100-A × (100/B)
From when using laminated porous film as secondary lithium batteries separator, obtain enough breathability, and anti-tablet Son is from the viewpoint of positive pole, negative pole are mixed into, below the μm of the aperture of P layer preferably 3, below more preferably 1 μm.
As it has been described above, the laminated porous film obtained is because breathability and excellent heat resistance and molten in P layer non-residual alcohol system Agent, it is possible to be preferably used as secondary lithium batteries separator.It addition, according to the laminated porous film manufacture method of the present invention, energy Enough not use the simple technique of coagulating bath to be easily manufactured laminated porous film.
Embodiment
Hereinafter, based on embodiment, the present invention carried out more specific description, but the present invention is not limited to these embodiments.
[embodiment 1]
As the perforated membrane of formation S layer, prepare Celgard company system " Celgard2500 ".This perforated membrane is by polypropylene structure Becoming, thickness is 25 μm, represents that the Gurley value (JIS standard P8117) of air permeability is 180 seconds/100cc.It follows that it is sub-as acyl Amine system coating fluid, prepares Unitika Co., Ltd. system " U imide varnish IP ".This coating fluid is to use to be obtained by DSC The aromatic polyamide acid imide that Tg is 280 DEG C as solute, use NMP and TEGM mixed solvent as solvent, do not contain There is the coating fluid of alcohol series solvent.It addition, solid component concentration is 15 mass %.Use rod coating machine at the one side of above-mentioned perforated membrane It is coated with this coating fluid, is dried 30 minutes in the stream of nitrogen gas of the non-humidified state of 140 DEG C, thus adds heat extraction solvent, obtain The P layer being made up of Porous polyamidoimide of thickness 8 μm is at the laminated porous film (L-1) of S layer surface integration.Will be to this The result that the characteristic of laminated porous film characteristic and P layer is evaluated is shown in table 1.
[embodiment 2]
The thickness of P layer is set to 4 μm, in addition, carries out similarly to Example 1, obtain laminated porous film (L-2). The result being evaluated the characteristic of this laminated porous film characteristic and P layer is shown in table 1.
[embodiment 3]
The thickness of P layer is set to 15 μm, in addition, carries out similarly to Example 1, obtain laminated porous film (L-3). The result being evaluated the characteristic of this laminated porous film and P layer is shown in table 1.
[embodiment 4]
Under a dry nitrogen atmosphere, in glass reaction vessel, DADE0.07 mole, MPD0.03 mole is loaded, Xiang Qi Middle addition NMP and triethylamine 0.1 mole, be stirred, and thus obtains the nmp solution that solid component concentration is 15 mass %.Its After, this solution is maintained at less than 10 DEG C, be under agitation slowly added dropwise the nmp solution of TMC 0.1 mole (solid constituent is dense simultaneously Degree: 20 mass %).After completion of dropwise addition, make solution return to room temperature, continue stirring 2 hours.The solution obtained is put in a large number Water in, produce polyamidoimide precipitation, this precipitation is filtered, clean and obtain the solid of yellow, afterwards at 200 DEG C Heat 12 hours, be dried and imidizate, thus obtain polyamidoimide powder body (AP).The Tg obtained by DSC of AP It it is 285 DEG C.It follows that dissolve AP in the mixed solvent of NMP and TEGM, obtain the polyamides that solid component concentration is 12 mass % Amine acid imide coating fluid (A-1).Here, the blending ratio of NMP Yu TEGM is set to TEGM amount is 70 relative to mixed solvent quality Quality %.Use coating fluid (A-1), be coated similarly to Example 1, obtain being made up of Porous polyamidoimide P layer (thickness is set to 3 μm) is at the laminated porous film (L-4) of S layer surface integration.By to this laminated porous film characteristic and P layer The result that characteristic is evaluated is shown in table 1.
[embodiment 5]
It is 80 mass % relative to mixed solvent quality that the blending ratio of NMP Yu TEGM is set to TEGM amount, in addition, Carry out similarly to Example 4, obtain polyamidoimide coating fluid (A-2) that solid component concentration is 12 mass %.Use Coating fluid (A-2), is coated similarly to Example 1, and (thickness sets to obtain the P layer that is made up of Porous polyamidoimide Be 3 μm) S layer surface integration laminated porous film (L-5).The characteristic of this laminated porous film characteristic and P layer will be commented The result of valency is shown in table 1.
[embodiment 6]
Prepare the Unitika Co., Ltd. system " U imide varnishSP " as imide series coating fluid.This coating fluid It is to use the aromatic polyimide that Tg is 225 DEG C obtained by DSC as solute, the mixed solvent work of use NMP and TEGM For solvent, the coating fluid that do not contains alcohol series solvent.It addition, solid component concentration is 15 mass %.Use rod coating machine above-mentioned This coating fluid of the single spreading of perforated membrane, is dried 30 minutes in the stream of nitrogen gas of the non-humidified state of 140 DEG C and adds heat extraction Solvent, obtains the P layer being made up of the Porous polyimides laminated porous film (L-6) in the integration of S layer surface of thickness 4 μm. The result being evaluated the characteristic of this laminated porous film characteristic and P layer is shown in table 1.
[embodiment 7]
Under a dry nitrogen atmosphere, in glass reaction vessel, load BPDA0.04 mole, ODPA0.06 mole, with NMP puts into together, after making solution, puts into the nmp solution of DADE0.1 mole, under stirring, be slowly added to BPDA0.04 mole, ODPA0.06 mole, react 4 hours at 50 DEG C, obtain the nmp solution (solid component concentration is 15 mass %) of polyamic acid. In this polyamic acid solution, add toluene, make the solution that solid component concentration is 13 mass %.This is heated molten at 200 DEG C Liquid, the carrying out along with reaction separates the imidization reaction that the moisture with toluene azeotropic is carried out 3 hours.Thereafter, Put in substantial amounts of water by evaporating the polyimide solution that toluene obtains, produce the precipitation of polyimides, this precipitation is filtered, After cleaning, pulverizing, heat 5 hours at 120 DEG C, thus obtain soluble polyimide powder body (BP).Powder body BP is obtained by DSC To Tg be 231 DEG C.It follows that dissolve powder body BP in the mixed solvent of DMAc and TEGM, obtaining solid component concentration is 12 The polyimide coating liquid (B-1) of quality %.Here the blending ratio of DMAc Yu TEGM is set to TEGM amount relative to mixed solvent Quality is 70 mass %.Use coating fluid (B-1), be coated with similarly to Example 6, obtain being made up of Porous polyimides P layer (thickness is set to 3 μm) is at the laminated porous film (L-7) of S layer surface integration.By to this laminated porous film characteristic and P layer The result that characteristic is evaluated is shown in table 1.
[embodiment 8]
It is 60 mass % relative to mixed solvent quality that the blending ratio of DMAc Yu TEGM is set to TEGM amount, except this with Outward, the coating fluid (B-2) that solid component concentration is 12 mass % is obtained similarly to Example 4.Use coating fluid (B-2), with Embodiment 7 similarly obtains the P layer being made up of the Porous polyimides stacking porous in the integration of S layer surface of thickness 3 μm Film (L-8).The result being evaluated the characteristic of this laminated porous film characteristic and P layer is shown in table 1.
[embodiment 9]
TEGM is set to TRGM, in addition, obtains the painting that solid component concentration is 12 mass % similarly to Example 7 Cloth liquid (B-3).Use coating fluid (B-3), obtain the P being made up of Porous polyimides of thickness 3 μm similarly to Example 7 Layer is at the laminated porous film (L-9) of S layer surface integration.By what the characteristic of this laminated porous film characteristic and P layer was evaluated Result is shown in table 1.
[comparative example 1]
The thickness of P layer is set to 25 μm, in addition, carries out similarly to Example 1, obtain laminated porous film (M-1). The result being evaluated the characteristic of this laminated porous film and P layer is shown in table 1.
[comparative example 2]
The polyamidoimide powder body (AP) used in example 4 is dissolved in NMP, and obtaining solid component concentration is 12 The polyamidoimide coating fluid (A-3) of quality %.Use coating fluid (A-3), be coated similarly to Example 1, obtain The P layer (thickness is set to 3 μm) being made up of polyamidoimide is at the laminated porous film (M-2) of S layer surface integration.Will be to this layer The result that the characteristic of folded perforated membrane characteristic and P layer is evaluated is shown in table 1.
[comparative example 3]
It is 25 mass % relative to mixed solvent quality that the blending ratio of NMP Yu TEGM is set to TEGM amount, in addition, Obtain polyamidoimide coating fluid (A-4) that solid component concentration is 12 mass % similarly to Example 4.Use coating fluid (A-4), it is coated similarly to Example 1, obtains the P layer (thickness is set to 3 μm) being made up of Porous polyamidoimide Laminated porous film (M-3) in the integration of S layer surface.The knot characteristic of this laminated porous film characteristic and P layer being evaluated Fruit is shown in table 1.
[comparative example 4]
The polyamidoimide powder body (AP) used in example 4 is dissolved in NMP and the mixing of tripropylene glycol (TPG) Solvent, obtains polyamidoimide coating fluid (A-5) that solid component concentration is 12 mass %.Here the mixing ratio of NMP Yu TPG It is 25 mass % relative to mixed solvent quality that rate is set to TPG amount.Use coating fluid (A-5), be coated with similarly to Example 1 Cloth, obtains the P layer (thickness is set to 3 μm) that is made up of the Porous polyamidoimide laminated porous film in the integration of S layer surface (M-4).The result being evaluated the characteristic of this laminated porous film characteristic and P layer is shown in table 1.
[comparative example 5]
The mixed solvent making the polyamidoimide powder body (AP) used in example 4 be dissolved in NMP and TPG is made poly- Amide imide coating fluid, it is desirable to obtain laminated porous film (M-5), but uniform solution cannot be obtained.Here NMP Yu TPG It is 70 mass % relative to mixed solvent quality that blending ratio is set to TPG amount.
[comparative example 6]
The polyimides powder body (BP) used in embodiment 7 is dissolved in the mixed solvent of DMAc and TPG, obtains solid Constituent concentration is the polyimide coating liquid (B-4) of 12 mass %.Here the blending ratio of DMAc with TPG be set to TPG amount relative It is 25 mass % in mixed solvent quality.Use coating fluid (B-4), be coated similarly to Example 1, obtain by polyamides sub- The P layer (thickness is set to 3 μm) that amine is constituted is at the laminated porous film (M-6) of S layer surface integration.Will be to this laminated porous film characteristic The result being evaluated with the characteristic of P layer is shown in table 1.
[comparative example 7]
Polyamides made by the mixed solvent making the polyimides powder body (BP) used in embodiment 7 be dissolved in DMAc and TPG Imines coating fluid, it is desirable to obtain laminated porous film (M-7), but uniform solution cannot be obtained.Here the mixing ratio of DMAc Yu TPG It is 70 mass % relative to mixed solvent quality that rate is set to TPG amount.
As shown in the Examples, for being formed by imide series high at the single or double of the porous layer being made up of polyolefin The laminated porous film of the present invention of the porous layer of molecular composition, the porous layer being made up of the imide series macromolecule of excellent heat resistance Being laminated in the surface of the porous layer being made up of polyolefin, the porosity of this heat-resisting porous layer is high, and good air permeability, so being laminated with The breathability of the laminated porous film of this heat-resisting porous layer is the most excellent.Additionally, this heat-resisting porous layer non-residual alcohol series solvent.Therefore, The laminated porous film of the present invention can be preferably used as secondary lithium batteries separator.
It addition, manufacturing method according to the invention, it is possible to obtain stacking with the simple operations utilizing heating to remove solvent many Pore membrane.Here, because not using the coagulating bath containing poor solvent, so not producing the waste liquid since coagulating bath.Therefore, ring Border adaptability is good.
[table 1]
Industrial applicability
The laminated porous film of the present invention is to have as such as secondary lithium batteries separator etc., the separator of charge storage element ?.

Claims (3)

1. a laminated porous film, it is characterised in that be the single or double of the porous layer being made up of polyolefin be formed by The laminated porous film of porous layer that imide series macromolecule is constituted, has a following characteristic:
1) air permeability is in terms of the Gurley value obtained based on JIS standard P8117, is 10 seconds/100cc～1000 seconds/100cc；
2) at the porous layer being made up of imide series macromolecule non-residual alcohol series solvent；
3) thickness of the porous layer being made up of imide series macromolecule is 1 μm～20 μm.
2. a secondary lithium batteries separator, is to use the laminated porous film described in claim 1.
3. the manufacture method of the laminated porous film described in a claim 1, it is characterised in that in the porous being made up of polyolefin The single or double coating of layer is made up of imide series macromolecule and the mixed solvent containing amide series solvent and ether series solvent Coating fluid and after forming film, add the solvent in film described in heat extraction, thus cause in film and be separated and form porous Layer, thus by the porous layer being made up of polyolefin and the porous layer stacking integration being made up of imide series macromolecule.
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