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WO1998038029A1 - Corps poreux de resine fluoree thermoplastique, procede pour la production de ce corps et utilisation de ce corps pour produire un element d'accumulateur - Google Patents

Corps poreux de resine fluoree thermoplastique, procede pour la production de ce corps et utilisation de ce corps pour produire un element d'accumulateur Download PDF

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Publication number
WO1998038029A1
WO1998038029A1 PCT/EP1997/004885 EP9704885W WO9838029A1 WO 1998038029 A1 WO1998038029 A1 WO 1998038029A1 EP 9704885 W EP9704885 W EP 9704885W WO 9838029 A1 WO9838029 A1 WO 9838029A1
Authority
WO
WIPO (PCT)
Prior art keywords
porous body
thermoplastic fluororesin
fluororesin porous
fine pores
sheet
Prior art date
Application number
PCT/EP1997/004885
Other languages
English (en)
Inventor
Takatoshi Kuratsuji
Kazuyoshi Ohashi
Yoshiyuki Miyaki
Original Assignee
Elf Atochem S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP9040392A external-priority patent/JPH09328566A/ja
Application filed by Elf Atochem S.A. filed Critical Elf Atochem S.A.
Publication of WO1998038029A1 publication Critical patent/WO1998038029A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
    • 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
    • H01M50/426—Fluorocarbon polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
    • B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/16—PVDF, i.e. polyvinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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

Definitions

  • thermoplastic fluororesin porous body a method for the production thereof and use of said porous body for producing a battery cell
  • the present invention relates to a thermoplastic fluororesin porous body, its method of production and a method of producing a cell.
  • the objectives are to offer a thermoplastic fluororesin porous body with outstanding resistance to chemicals, which is light in weight and excellent in terms of mechanical strength and mass transfer properties, together with a method for the production thereof, and a method for producing a cell employing this porous body.
  • thermoplastic fluororesins are used for coating materials and for electrical/electronic components, steel pipe linings, chemical plant components and weather- resistant/stain-resistant films, etc.
  • fluororesins generally have a high specific gravity and so, in the form of moulded articles, they have the disadvantage of being heavy.
  • Japanese Unexamined Patent Publication Nos 61-242602 and 3-215535 etc
  • the method of blending an extractable resin and then forming a film after which the resin is extracted Japanese Unexamined Patent Publication No. 57-10888, etc
  • the method of mixing-in an elutable filler, then moulding/ sintering, after which the filler is eluted Japanese Unexamined Patent Publication No. 51-134761 , etc
  • the method in which a poorly-compatible resin is blended and then film formation conducted, after which drawing is performed and cracks are produced at the interface between the poorly-compatible resin and the matrix resin, and porosity thereby produced Japanese Unexamined Patent Publication No.
  • separators employed in lithium cells of batteries or other such non-aqueous type cells these have the role of preventing short-circuiting between the positive and negative electrodes, or of ensuring conductivity by retaining electrolyte in the numerous pores introduced in the separator.
  • PE polyethylene
  • PP polypropylene
  • PE and PP are combustible materials and, especially in lithium batteries, a more highly safe material is required.
  • lithium batteries which use, as the separator, vinylidene fluoride copolymer film which has been swollen by means of a solution formed by dissolving a Li salt such as LiPF6 in a carbonate solvent
  • a Li salt such as LiPF6
  • a carbonate solvent Japanese Unexamined Patent Publication Nos 8-507407 and 8-509100.
  • the vinylidene fluoride copolymer film swollen with solvent either has insufficient temperature resistance at high temperatures (50°C and above) or the low temperature (0°C and below) characteristics of the cell, such as capacity, tend to be lowered.
  • the present invention has been made as a result of research to overcome the disadvantages of conventional PVDF type porous bodies and cell separators, and to obtain a PVDF porous body which is light and has excellent mechanical strength by a physical method, without employing solvents or additives, and also to obtain a battery separator and a cell employing said porous body.
  • the present invention is a thermoplastic fluororesin porous body which is characterized in that it comprises a thermoplastic fluororesin containing at least 90 wt% vinylidene fluoride as resin structural units, and has flattened pores of width (minor axis) 0.1 to 3 ⁇ m and length (major axis) 0.5 to 20 ⁇ m; a method of producing a thermoplastic fluororesin porous body which is characterized in that polyvinylidene fluoride is melt extruded in a sheet form or hollow form, after which, having optionally raised the degree of crystallization to at least 40% by heat-treatment, it is cold drawn and numerous flattened fine pores produced, by means of which the apparent specific gravity is made no more than 1.7; a battery separator comprising said porous body, and a method of producing a cell employing same.
  • thermoplastic fluororesin is a thermoplastic fluororesin containing at least 90 wt%, and preferably at least 95 wt%, vinylidene fluoride as resin structural units.
  • thermoplastic fluororesin may be a copolymer containing other component(s) in a range up to 10 wt%. If the percentage copolymerization exceeds 10 wt%, it is difficult to obtain the porous body of the present invention.
  • copolymerizable components there are tetrafluoroethylene, trifluoroethylene, trifluorochloro-ethylene, vinyl fluoride, hexafluoro- propylene, ethylene, perfluoroalkyl vinyl ether and the like.
  • This thermoplastic fluororesin is obtained by emulsion polymerization, suspension polymerization or other such generally-employed polymerization method, and the MFR value is preferably from 0.1 to 500 g/10 minutes.
  • thermoplastic fluororesin of the present invention a small amount of other polymer can be blended with the thermoplastic fluororesin of the present invention and, moreover, there can be freely included conventionally-known antioxidants, thermal decomposition preventives, UV absorbers, hydrolysis resistance improvers, colouring agents (dyes, pigments), antistatic agents, electrical conductors, crystallization nucleating agents, crystallization promoters, plasticizers, ready-slip agents, lubricants, release agents, flame retarders, flame retarding auxiliaries, reinforcing agents, fillers, adhesion auxiliaries, adhesive agents and the like.
  • antioxidants antioxidants
  • thermal decomposition preventives UV absorbers
  • hydrolysis resistance improvers colouring agents (dyes, pigments), antistatic agents, electrical conductors, crystallization nucleating agents, crystallization promoters, plasticizers, ready-slip agents, lubricants, release agents, flame retarders, flame retarding auxiliaries, reinforcing agents, fillers, adhesion aux
  • the porous body of the present invention has flattened fine pores of width (minor axis) 0.1 to 3 ⁇ m and length (major axis) 0.5 to 20 ⁇ m. If the size of the fine pores is too small, then it is difficult to achieve a specific gravity reducing effect while, conversely, if it is too large then the filtering effect and the mechanical strength are impaired.
  • the width is preferably 0.2 to 2 ⁇ m and length 0.5 to 15 ⁇ m.
  • the apparent specific gravity of the porous body of the present invention is preferably no more than 1.7. More preferably, it is no more than 1.6 and no less than 1.2.
  • the apparent specific gravity can be lowered further by raising the fine pore size or increasing the number of pores but, not only is this technically difficult, it is also undesirable in terms of the membrane performance and strength.
  • the porous body of the present invention is mainly a sheet form or hollow form material.
  • “Sheet form material” here encompasses the range from a thick plate (mm order) to a thin film ( ⁇ m order).
  • a “hollow form material” means the range from a thick pipe to a fine tube, or a hollow fibre or blown film, etc.
  • the porous body of the present invention can be produced by melt extrusion of the thermoplastic fluororesin above its melting point and below its decomposition temperature, then cooling and solidifying, followed by careful cold drawing.
  • other methods can also be used such as injection moulding and rotary moulding, etc.
  • the draw ratio will depend on the type of resin (percentage copolymerization) and the extrusion and cooling conditions, and will be a factor of from 1.1 to 6, but less than the draw ratio at break, and preferably from 1.2 to 4.
  • the drawing may be either uniaxial or biaxial (simultaneous or consecutive) but, in the case of multistage drawing, care is needed because there is a tendency for the shape of the fine pores to be determined for the most part by the conditions in the first stage.
  • the porous body of the present invention is not readily obtained by hot drawing.
  • the porous body of the present invention can be produced still more readily by performing a heat treatment prior to drawing and thereby raising the degree of crystallization to at least 40%. It is further preferred that the structure be fixed by another heat treatment following the cold drawing.
  • the recommended heat treatment temperature is 70 to 155°C, and preferably 100 to 150°C.
  • the heat treatment can be conducted in a free state, or alternatively it may be carried out with the shrinkage being restricted, at a fixed length or while being stretched. However, in the stretched state, the percentage stretch should be no more than 10%, and preferably no more than 5%. In short, it is carried out within a range such that the spherulites generated at the time of solidification of the melt are not destroyed, and preferably these are allowed to grow in the state prior to their breakdown and transition to crystallites.
  • the tensile strength was the value obtained when the breaking strength of a strip-shaped sample of width cut to 15 mm, measured at an extension rate of 50 mm/min based on a gauge length of 50 mm, was divided by the cross-sectional area prior to extension.
  • the tensile elongation refers to the extension at break.
  • Vinylidene fluoride homopolymer of MFR 11 was melted at 240°C using a single screw extruder fitted with a 15 cm wide T-die at the tip, and then extruded as a sheet of thickness about 200 ⁇ m onto a cooling drum of surface temperature 20°C. The degree of crystallization of this sheet was 38%. (Hereinafter this is referred to as the base sheet.) This sheet was subjected to uniaxial drawing by a factor of 2.5 between two rolls at room temperature (23°C). The two edges showed slight necking, and a somewhat whitened film of thickness 105 ⁇ m was obtained.
  • Example 1 When the base sheet obtained in Example 1 was heat treated at a fixed length for 30 minutes at 130°C, the degree of crystallization became 45%. Film of thickness about 120 ⁇ m obtained by drawing this sheet by a factor of 2.1 at room temperature had an apparent specific gravity of 1.58 and a tensile strength and elongation of 140 MPa and 110%. When viewed under a microscope numerous comparatively uniform, flattened, fine pores of width about 1 ⁇ m and length 5 - 10 ⁇ m were observed. Comparative Example 1
  • Example 3 T Comparative Example 2
  • Polyvinylidene fluoride Polyvinylidene fluoride
  • a positive electrode was obtained in the following manner. 100 parts by weight of LiCoO2, as the positive electrode active material, and 6 parts by weight of graphite, as a conducting agent, were dispersed in N-methylpyrrolidone along with 10 parts by weight of polyvinylidene fluoride as a binder, to form a slurry (paste). This slurry was applied to both faces of aluminium foil of thickness 20 ⁇ m and left for 1 hour at 120°C, after which it was dried under reduced pressure and pressed, and a positive electrode of thickness 175 ⁇ m and width 20 mm obtained.
  • LiCoO2 as the positive electrode active material
  • graphite as a conducting agent
  • a charging/discharging test was carried out by initially charging up to 4.1 V at a current density of 30 mA per 1g of carbon and then discharging down to 2.5 V at the same current density. The second time, and thereafter, charging and discharging were again repeated under the same conditions and the cell evaluated according to the discharge capacity. As a result, the discharge capacity on the 100th cycle was good, being over 60% that on the 10th cycle.
  • the porous body of the present invention is useful as a filter or other such filtration material, and as a separation membrane such as separator for a battery, etc. Moreover, it can serve as a base material for membranes with added functionality, by supporting ion-exchange groups or adsorbent materials.
  • the porous body of the present invention when applied to lithium cells/batteries, can be used as a separator or as an electrode by complexing with an electrode active material.
  • the porous film is impregnated with an electrolyte solution formed by dissolving at least one type of lithium salt selected from LiPF ⁇ , UBF4, UCIO4, LiAsF ⁇ , LiN(CF3SO2)2, UCF3SO3, LiSbF ⁇ and the like, in a suitable solvent (chiefly a carbonate such as ethylene carbonate, propylene carbonate or dimethyl carbonate, etc).
  • the porous body can be used as a support for a gel electrolyte (polymer gel swollen with a solution containing electrolyte).
  • the porous body of the present invention can be used as a separator or electrode support in nickel/ hydrogen batteries, silver/zinc batteries, lead/acid batteries, zinc/air batteries, nickel/cadmium batteries, alkali batteries or zinc bromide batteries, etc.
  • the porous body of the present invention is light in weight and outstanding in its mechanical characteristics, and it is valuable for various kinds of filtration materials and for separating membranes, etc.
  • the separator when employed as the separator in a lithium cell, etc, since the PVDF is poorly combustible, it forms a battery which is safer than in the case where a polyethylene separator is used.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Cell Separators (AREA)

Abstract

La présente invention concerne un corps poreux de résine fluorée thermoplastique léger, et présentant des caractéristiques importantes telles que des propriétés mécaniques, sans utiliser de matériel ou de procédé spécial. L'invention traite également d'un élément d'accumulateur utilisant ce corps poreux. Le corps poreux de résine fluorée thermoplastique est obtenu par extrusion, d'une résine fluorée thermoplastique fondue sous forme de feuille ou de forme creuse, opération après laquelle le degré de cristallisation est éventuellement augmenté d'au moins 40 % par un traitement thermique. Après ce traitement, la résine fluorée est étirée à froid, et de nombreux pores fins aplatis sont obtenus, au moyen desquels la densité relative apparente ne dépasse pas 1,7. Dans l'élément d'accumulateur, le corps poreux de résine fluorée thermoplastique susmentionné peut être fabriqué pour la construction du séparateur et/ou d'au moins une des électrodes.
PCT/EP1997/004885 1997-02-25 1997-08-28 Corps poreux de resine fluoree thermoplastique, procede pour la production de ce corps et utilisation de ce corps pour produire un element d'accumulateur WO1998038029A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/40392 1997-02-25
JP9040392A JPH09328566A (ja) 1996-03-01 1997-02-25 熱可塑性フッ素系樹脂多孔体、その製造方法、および電池の製造方法

Publications (1)

Publication Number Publication Date
WO1998038029A1 true WO1998038029A1 (fr) 1998-09-03

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PCT/EP1997/004885 WO1998038029A1 (fr) 1997-02-25 1997-08-28 Corps poreux de resine fluoree thermoplastique, procede pour la production de ce corps et utilisation de ce corps pour produire un element d'accumulateur

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0994521A1 (fr) * 1998-10-16 2000-04-19 Sony Corporation Batterie à électrolyte solide
EP1369168A4 (fr) * 2001-03-06 2004-08-18 Asahi Chemical Ind Procede de fabrication d'une pellicule de fil creux
WO2005035641A1 (fr) * 2003-09-12 2005-04-21 3M Innovative Properties Company Films pvdf microporeux et procede de fabrication
EP1189299A3 (fr) * 2000-09-18 2006-12-27 Sony Corporation Batterie secondaire
US7381666B2 (en) 2002-12-20 2008-06-03 Kimberly-Clark Worldwide, Inc. Breathable film and fabric having liquid and viral barrier
WO2010020115A1 (fr) * 2008-08-22 2010-02-25 清华大学 Procédé de préparation de membrane en fibres creuses de fluorure de polyvinylidène de phase cristalline bêta
US7909178B2 (en) 2006-08-10 2011-03-22 Kuraray Co., Ltd. Porous membrane of vinylidene fluoride resin and process for producing the same

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JPS4998880A (fr) * 1973-01-16 1974-09-18
GB1553050A (en) * 1977-01-27 1979-09-19 Kureha Chemical Ind Co Ltd Process for producing microporous tube of a vinylidene fluoride polymer
JPS596231A (ja) * 1982-07-05 1984-01-13 Mitsubishi Rayon Co Ltd フッ素樹脂多孔質膜の製造方法
JPS61146811A (ja) * 1984-12-21 1986-07-04 Ube Ind Ltd 多孔質熱可塑性樹脂中空糸の製造法
JPS6233878A (ja) * 1985-08-06 1987-02-13 三菱レイヨン株式会社 耐熱性多孔質ポリオレフイン中空糸
JPH02212528A (ja) * 1989-02-13 1990-08-23 Sumitomo Electric Ind Ltd 多孔性分離膜の製造方法
WO1995015589A1 (fr) * 1993-11-30 1995-06-08 Bell Communications Research, Inc. Element de batterie rechargeable a ions de lithium, activable par l'electrolyte, et procede de fabrication
JPH07161350A (ja) * 1993-12-08 1995-06-23 Fuji Elelctrochem Co Ltd リチウム電池用電極スラリーの製造方法

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JPS4998880A (fr) * 1973-01-16 1974-09-18
GB1553050A (en) * 1977-01-27 1979-09-19 Kureha Chemical Ind Co Ltd Process for producing microporous tube of a vinylidene fluoride polymer
JPS596231A (ja) * 1982-07-05 1984-01-13 Mitsubishi Rayon Co Ltd フッ素樹脂多孔質膜の製造方法
JPS61146811A (ja) * 1984-12-21 1986-07-04 Ube Ind Ltd 多孔質熱可塑性樹脂中空糸の製造法
JPS6233878A (ja) * 1985-08-06 1987-02-13 三菱レイヨン株式会社 耐熱性多孔質ポリオレフイン中空糸
JPH02212528A (ja) * 1989-02-13 1990-08-23 Sumitomo Electric Ind Ltd 多孔性分離膜の製造方法
WO1995015589A1 (fr) * 1993-11-30 1995-06-08 Bell Communications Research, Inc. Element de batterie rechargeable a ions de lithium, activable par l'electrolyte, et procede de fabrication
JPH07161350A (ja) * 1993-12-08 1995-06-23 Fuji Elelctrochem Co Ltd リチウム電池用電極スラリーの製造方法

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6537704B1 (en) 1998-10-16 2003-03-25 Sony Corporation Solid electrolyte battery
US7763376B2 (en) 1998-10-16 2010-07-27 Sony Corporation Solid electrolyte battery
EP0994521A1 (fr) * 1998-10-16 2000-04-19 Sony Corporation Batterie à électrolyte solide
EP1189299A3 (fr) * 2000-09-18 2006-12-27 Sony Corporation Batterie secondaire
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