WO1997035350A1 - Procede de stratification d'un film electrolyte polymere solide - Google Patents

Procede de stratification d'un film electrolyte polymere solide Download PDF

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Publication number
WO1997035350A1
WO1997035350A1 PCT/JP1997/000945 JP9700945W WO9735350A1 WO 1997035350 A1 WO1997035350 A1 WO 1997035350A1 JP 9700945 W JP9700945 W JP 9700945W WO 9735350 A1 WO9735350 A1 WO 9735350A1
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WIPO (PCT)
Prior art keywords
polymer electrolyte
solid polymer
laminate
film
laminating
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Application number
PCT/JP1997/000945
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English (en)
Inventor
Junji Yotsuyanagi
Motoyuki Hirata
Original Assignee
Showa Denko K.K.
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Publication date
Application filed by Showa Denko K.K. filed Critical Showa Denko K.K.
Publication of WO1997035350A1 publication Critical patent/WO1997035350A1/fr
Priority to US08/946,882 priority Critical patent/US5972054A/en

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Classifications

    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
    • 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
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method for laminating a solid polymer electrolyte film and a method for laminating the film on an electrode.
  • a solid polymer electrolyte (hereinafter referred to as a "SPE") is a polymer substance which exhibits a high ion conductivity in the solid state, and the application thereof to various sensors and fuel cells is anticipated. Furthermore, the SPE can be applied to a next generation battery, a photoelectric cell or an electrochro ic element.
  • the SPE In order to impart high ion conductivity to a SPE, the SPE must have a low glass transition temperature. However, when the glass transition temperature is low, the film strength is lowered which makes the SPE difficult to handle in an industrial environment.
  • the above-described method encounters difficulty in controlling the polymerization degree of the SPE or the thickness of the SPE film, and a homogenous and uniform SPE film can hardly be obtained.
  • a SPE may have a water- bsorbing property depending on the kind of SPE
  • the atmosphere should be controlled in order to control the water content during the step of compositing the SPE and an electrode.
  • the present invention has been accomplished under the above-mentioned circumstances, and an object of the present invention is to provide a homogeneous SPE composite film and a method for producing the composite film. Another object of the present invention is to provide amethod for laminating a SPE film on an electrode in a simple and easy manner. Yet another object of the present invention is to provide a method for producing a SPE composite electrode.
  • the present inventors have developed a method for producing a SPE composite film of homogeneous ion conductivity and uniform thickness by compositing a SPE layer comprising a SPE material having a low glass transition temperature and a high ion conductivity with a base film, and a method for producing a SPE laminate film of good shelf-life which comprises a SPE film derived from the SPE composite film as a constituent structural member.
  • the present inventors have also developed a method for laminating a SPE film on an electrode by using the SPE laminate film and a method for producing a SPE composite electrode.
  • the present invention provides a convenient method for producing a SPE laminate film comprising a base film such as those made of plastic and a SPE layer ("SPE laminate film” is hereinafter referred to as a "composite film”) , for producing a composite film comprising a base film, a SPE layer and a cover film.
  • the present invention also provides a method for producing a SPE composite electrode using a composite film of the present invention, more specifically, a method for producing a SPE composite electrode in which a SPE film having a base film thereon is laminated on an electrode.
  • the method comprises laminating the SPE surface opposite the base film of the composite film, or laminating the SPE surface from which a cover film is removedwhen the composite film has a cover film, on an electrode previously coated with a curable adhesive such that the SPE surface contacts the electrode, andthencuring the adhesive.
  • Thepresent invention also provides a method for producing a SPE composite electrode which comprises providing a SPE composite electrode in which a SPE film having a base film thereon is laminated on an electrode as described above, removing the base film, and laminating a second constituent structural member such as another electrode on the exposed SPE surface.
  • the present invention provides the followingmethods for laminatingaSPE film (methods forproducing a composite film) and methods for producing a SPE composite electrode:
  • a method for laminating a SPE film which comprises laminating a layer of a fluid SPE on a base film or on a thin layer comprising a metal or a metal oxide which is laminated on a base film, andapplyingpressure to the resulting laminatewith a force applied on the upper surface of the laminate and a force in opposition thereto applied on the lower surface of the laminate;
  • a method for laminating a SPE film which comprises laminating a layer of a fluid SPE on a base film or on a thin layer comprising a metal or a metal oxide which is laminated on a base film, followed by laminating a cover film on a surface of said fluid SPE layer, and applying pressure to the resulting laminate with a force applied on the upper surface of the laminate and a force in opposition thereto applied on the lower surface of the laminate;
  • (3) a method for laminating a SPE film which comprises laminating a layer of a fluid SPE containing a polymerizable compound on a base film or on a thin layer comprising a metal or ametal oxide which is laminated on a base film, polymerizing said polymerizable compound, thereby making said SPE layer substantially non-flowable, and applying pressure to the resulting laminate with a force applied on the upper surface of the laminate and a force in opposition thereto appliedon the lower surface of the laminate;
  • a method for laminating a SPE film which comprises laminating a layer of a fluid SPE containing a polymerizable compound on a base film or on a thin layer comprising a metal or a metal oxide which is laminated on a base film, followed by laminating a cover film on a surface of said fluid SPE layer, polymerizing said polymerizable compound, therebymaking the SPE layer substantially non-flowable, and applying pressure to the resulting laminate with a force applied on the upper surface of the laminate anda force in opposition thereto appliedon the lower surface of the laminate;
  • a method for producing a SPE composite electrode which comprises providingaSPE filmin theformof alaminateconsisting of a SPE layer, a base film and a cover film or consisting of a SPE layer, a base film having said thin layer thereon and a cover film as described in items (2) or (4) above, removing the cover film from the SPE layer of said laminate, laminating the SPE surface of said laminate on an electrode previously coated with a curable adhesive such that the SPE surface contacts the electrode, and then curing the adhesive;
  • a method for producing a SPE composite electrode which comprises providing a SPE film in the formof a laminate consisting of a SPE layer and a base film or consisting of a SPE layer and a base filmhaving said thin layer thereon according to the method described in items (1) or (3) above, followed by laminating the SPE surface of said laminate on an electrode previously coated with a curable adhesive such that the SPE surface contacts the electrode, curing the adhesive, then removing the base film or the base film having said thin layer thereon to expose a surface of said SPE layer, and laminating another constituent structural member on the exposed surface of said SPE;
  • (9) a method for producing a SPE composite electrode which comprises providing a SPE filmin the formof a laminate consisting of a SPE layer, a base film and a cover film or consisting of a SPE layer, a base film having said thin layer thereon and a cover film according to the method described in items (2) or (4) above, followed by removing the cover film from the SPE layer of said laminate, laminating the SPE surface of said laminate on an electrode previously coatedwith a curable adhesive such that the SPE surface contacts the electrode, thencuring the adhesive, then removing the base film or the base film having said thin layer thereon to expose a surface of said SPE layer, and laminating another constituent structural member on the exposed surface of said SPE;
  • (10) a method for producing a SPE composite electrode which comprises providing a SPE filmin the formof a laminateconsisting of a SPE layer and a base film or consisting of a SPE layer and a base film having said thin layer thereon according to the method described in items (1) or (3) above, laminating the SPE surface of said laminate on an electrode previously coated with a curable adhesive such that the SPE surface contacts the electrode, curing the adhesive, then removing the base film or the base film having said thin layer thereon to expose a surface of said SPE layer, and laminating a second electrode on the exposed SPE surface; and
  • a method for producing a SPE composite electrode which comprises providing a SPE film in the formof a laminate consisting of a SPE layer, a base film and a cover film or consisting of a SPE layer, a base film having said thin layer thereon and a cover film according to the method described in items (2) or (4) above, followed by removing the cover film from the SPE layer of said laminate, laminating the SPE surface of said laminate on an electrode previously coatedwith a curable adhesive such that the SPE surface contacts the electrode, then curing the adhesive, then removing the base film or the base film having said thin layer thereon to expose a surface of said SPE layer, and laminating a second electrode on the exposed SPE surface.
  • the base film for use in the present invention preferably includes various water-proof plastic films.
  • various water-proof plastic films include general thermoplastic resins such as polyolefins including polyethylene and polypropylene, polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyamides such as nylon-6 and nylon-6,6.
  • the film may either be an unstretched film or a stretched film.
  • the thickness of the base film is suitably from 1 to 5,000 ⁇ m, preferably from 1 to 1,000 ⁇ m, and more preferably from 5 to 100 ⁇ m.
  • the base film for use in the present invention preferably also includes a laminate film comprising the above-mentionedbase film having laminated thereon a metal or metal oxide such as aluminum, alumina and silica by a known method such as vapor deposition.
  • a metal or metal oxide such as aluminum, alumina and silica by a known method such as vapor deposition.
  • other films can be used as long as they can be readily removed from a SPE. Examples thereof include a metal foil such as aluminum foil, stainless steel foil and copper foil.
  • the SPE foruse in the present invention comprises apolymer substance obtained by polymerizing a polymerizable compound in the presence or absence of an electrolyte salt.
  • the mobility of an electrolyte ion in the SPE is high in the presence of at least one electrolyte salt, thereby providing an ion conductivity of lO ' ⁇ cm "1 or greater, preferably lO ⁇ cm '1 or greater, and more preferably lO ⁇ cm "1 or greater.
  • the SPE material for use in the present invention includes not only an SPE containing an electrolyte salt and having an ion conductivity within the above-mentioned range, but also a SPE which provides an ion conductivity within the above-mentioned range when an electrolyte salt and/or solvent that is later added to the SPE contained in a SPE composite electrode that is produced using the composite film of the present invention, or in an electrochemical apparatus such as a battery or capacitor that is produced using the SPE composite electrode of the present invention.
  • Polymerization may be performed by thermal polymerization or a known method by exposing with active light such as visible light, ultraviolet light, electron beams, ⁇ rays or X rays.
  • Examples of the polymerizable compound include functional monomers and oligomers having at least one hetero atom.
  • the compound represented by the above-described formula examples include N-methacryloylcarbamic acid ⁇ -methyl oligooxyethyl ester and methacryloyloxyethylcarbamic acid ⁇ -methyl oligooxyethyl ester.
  • These polymerizable compounds maybeusedindividuallyor inacombinationof twoormore thereof.
  • oxyalkylene chain-containing urethane (meth)acrylate, urethane acrylate, oxyalkylene chain-containing (meth)acrylic ester and (meth)acrylamide-base compounds are preferred.
  • Oxyalkylene chain-containing urethane (meth)acrylate is more preferred.
  • At least one polyfunctional polymerizable compound is preferably used in combination with another polymerizable compound.
  • ... (meth)acryl... is a generic term including "...methacryl... " and “ ...acryl... "
  • alkyleneoxy” and “oxyalkylene” have the same meaning.
  • the glass transition temperature of the SPE material is not the glass transition temperature of the polymeric substance constituting the SPE material. Rather, it is the glass transition temperature of a composite material which comprises, in addition to the polymer substance, at least one member selected from the group consisting of a plasticizer, a solvent, a polymerizable compound or an oligomer thereof and an electrolyte salt. Therefore, the SPE material of the present invention includes, in addition to the polymer that is obtained from the above-mentioned polymerizable compound, those having a glass transition temperature of room temperature or lower by adding a plasticizer, solvent, etc. , even if the substance itself has a glass transition temperature that is higher than room temperature, such as polyacrylonitrile.
  • the term "having a high ion conductivity" as used herein means that the ion conductivity is lO ⁇ cm "1 or greater, preferably lO ⁇ cm "1 or greater, and more preferably lO' ⁇ 1 cm "1 or greater.
  • the electrolyte salt include LiC10 4 , LiBF 4 , LiAsF 6 , LiCF 3 S0 3 , LiPF 6 , Lil, LiBr, LiSCN. LiN(CF 3 S0 2 ) 2 , Nal, Li 2 B 10 Cl 10 .
  • Li salts such as LiC10 4 and LiPF 6 and quaternary ammonium salts such as (C 2 H S ) 4 NC10 4 are preferred.
  • the blendingratio of the electrolyte salt is generallyfrom 0.1 to 70 parts byweight, preferably from 1 to 50 parts byweight, more preferably from 1 to 30 parts by weight, per 100 parts by weight of the polymerizable compound.
  • a plasticizer, a solvent, apolymerization initiator or the like may be blended into the SPE of the present invention, if desired.
  • the plasticizer or solvent include tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4,4- dimethy1-1,3-dioxane, ⁇ -butyrolactone, ethylene carbonate, propylene carbonate, butylene carbonate, sulfolane, 3- methylsulfolane, t-butyl ether, i-butyl ether, 1,2- dimethoxyethane, 1,2-diethoxymethoxyethane, methyldiglyme, methyltriglyme, methyltetraglyme, ethylglyme and ethyldiglyme. These compounds may be used individually or in combination of two or more thereof.
  • the polymerization initiator examples include a radical thermal polymerization initiator such as azobisisobutyronitrile andbenzoylperoxide, aradialphotopolymerization initiator such as benzyl methyl ketal and benzophenone, a cationic polymerization catalyst such as a protonic acid (e.g., CF 3 COOH) and a Lewis acid (e.g. , BF 3 , A1C1 3 ) , and an anionic polymerization catalyst such as butyl lithium, sodium naphthalene and lithium alkoxide.
  • a radical thermal polymerization initiator such as azobisisobutyronitrile andbenzoylperoxide
  • aradialphotopolymerization initiator such as benzyl methyl ketal and benzophenone
  • a cationic polymerization catalyst such as a protonic acid (e.g., CF 3 COOH) and a Lewis acid (e.g. , BF 3
  • the thickness of the SPE film (layer) of the present invention is generally from 0.1 to 1,000 ⁇ m, preferably from 0.1 to 300 ⁇ m, more preferably from 0.1 to 50 ⁇ m.
  • the base film for use in a composite film of the present invention should have good wettability to the SPE or fluid SPE at the time of forming the composite film.
  • the SPE composite electrode has a base film thereon and is used for laminating another constituent structural member such as a second electrode on the exposed SPE surface by removing the base film, the base filmshouldhave goodremovabilityfromthe SPE filmlayer.
  • the base film should be removable without deforming the shape of the SPE film. Accordingly, it is preferable to form (laminate) a thin layer comprising a metal or a metal oxide on the base film surface, on which the SPE is laminated.
  • the metal or metal oxide thin film may be a thin film generally used for improving the gas barrierproperty of aplastic film.
  • a thin film generally used for improving the gas barrierproperty of aplastic film.
  • Specific examples thereof include a foil of or a film evaporated with a metal such as aluminum, stainless steel or copper, and a film evaporated with a metal oxide such as silica or alumina.
  • a metal oxide such as silica or alumina.
  • an aluminumfoil, an aluminum-evaporated film, a silica-evaporated film and an alumina-evaporated film are preferred.
  • the thickness of the thin film is not particularly limited, however, in the case of a foil, it is preferably from 5 to 100 ⁇ m and in the case of an evaporated film, from 50 to 2,000A.
  • Preferred examples of the composite film in the present invention include (a) a structure in which the SPE layer is laminated on the surface of a base film, (b) a structure in which the SPE film is laminated on a thin layer comprising a metal or a metal oxide laminated on a base film, and (c) a structure in which a cover film is laminated on the side of the SPE film layer opposite the base film of either of the above composite film (a) and (b) , and any of these is optionally selected depending on the use.
  • the composite film is preferably used in a method for producing a SPE composite electrode which comprises laminating a fluid SPE (or a fluid SPE precursor material) on a base film ora thin layercomprising ametal ormetal oxidewhichis laminated on a base film by an optionally selected method such as coating, spraying, anddipping, and if necessary, causing apolymerization reaction, thereby making the SPE substantially non-flowable.
  • the composite film has a structure which comprises a cover film
  • it can be produced by (i) a method comprising laminating a cover film after laminating a SPE film layer on a base film or a base film having a thin layer comprising a metal or a metal oxide laminated thereon as described above, (ii) a methodcomprisinglaminatingthe SPEon acoverfilmsubstantially in a non-flowable state, in a similar manner as described above, and then laminating thereon a base film or a base film having a thin layer comprising a metal or a metal oxide laminated thereon, or (iii) a method comprising laminating a fluid SPE (or a fluid SPE precursor material) between a base film or a base film having a thin layer comprising ametal or a metal oxide laminated thereon and a cover film, and then if necessary, causing a polymerization reaction, thereby making the SPE a substantially non-flowable film.
  • fluidSPE and fluidSPEprecursormaterial each includes not onlyaflowable stateSPEandaSPEprecursormaterial, respectively, at room temperature (20°C) under atmospheric pressure, but also those which are flowable at room temperature under a pressure of 50 kgf/cm 2 or lower.
  • the fluid SPE as usedin themethoddescribedinitems (1) or (2) above preferably does not flow when laminated on a base film or a thin layer comprising a metal or a metal oxide laminated on a base film at room temperature and under atmospheric pressure during a period of one hour, but is flowable over a period that is longer than one hour at room temperature and under atmospheric pressure or is flowable under a pressure that is higher than atmospheric pressure and 50 kgf/cm 2 or lower.
  • a cover film is preferably laminated thereon by means of, for example, nip rolls.
  • the cover film is not particularly limited, and the above-described plastic film which can be used as a base film may be appropriately used, and a film which is easily removed from the SPE film is preferably used.
  • the composite film according to the present invention comprises a cover film
  • pressure is preferably applied to the SPE laminate film with a force applied on the upper surface of the laminate and a force in opposition thereto applied on the lower surface of the laminate in the method described in (i), (ii) or (iii) above so that the thickness of the SPE film in the composite film canbe controlled.
  • Any conventional press methods can be used as a pressurization method.
  • a general pressuremoldingmethod suchas amethodusing nip rolls is preferably used, and a method for continuously producing the composite film is a particularly preferred embodiment of the present invention.
  • the pressurization pressure can be a pressure used in a conventional laminate molding, and therefore is not particularly limited. Generally, pressurization is effected under a pressure of 50 kgf/cm 2 or lower as generally used in low pressure molding, as long as the thickness of the SPE film can be controlled to a desired thickness. For example, when nip rolls are used, the pressure is not specifically limited so long as the pressing provides the desired thickness and does not adversely affect the performance of the composite film. For instance, a roll pressure between 1 to 30 kgf/cm 2 is preferred, and 5 to 10 kgf/cm 2 is more preferred.
  • examples of the negative electrode include lithium metals, lithium alloys such as lithium/aluminum alloy, lithium/lead alloy and lithium/antimony alloy, and when Li ion is usedas acarrier, theelectrodemaycomprise acarbonmaterial.
  • the positive electrode examples include metal oxides such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide and molybdenum oxide, metal sulfides such as molybdenum sulfide, titanium sulfide and vanadium sulfide, electroconductive polymers such as polyacetylene and derivatives thereof, polyparaphenylene and derivatives thereof, polypyrrole and derivatives thereof, and polythienylene and derivatives thereof, natural graphite, artificial graphite, vapor phase process graphite, petroleumcoke, coal coke, fluorinatedgraphite, pitch-base carbon, polyacene and carbon materials.
  • metal oxides such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide and molybdenum oxide
  • metal sulfides such as molybdenum sulfide, titanium sulfide and vanadium sulfide
  • electroconductive polymers such as polyacetylene and derivatives thereof, polyparaphenylene and
  • the curable adhesive for use in the present invention examples include the above-described polymerizable compounds and fluid mixtures containing the polymerizable compound.
  • the curable adhesive is not limited to such compositions.
  • the adhesive can be coated onto the electrode by a known method such as coating, spraying, and dipping the adhesive on the electrode.
  • electrode previously coated with a curable adhesive means that one of the surfaces of the electrode is previously covered by a curable adhesive, and the electrode may ormaynot be impregnatedwith the curable adhesive.
  • a SPE composite electrode is prepared by providing a SPE film having a base film laminated thereon (composite film), laminating the SPE surface opposite the base film (or a SPE surface which is exposed while removing a cover film therefrom when the composite film comprises a cover film) on an electrode previously coated with a curable adhesive such that the exposed SPE surface contacts the electrode, and then curing the adhesive.
  • a SPE composite electrode having a SPE film of a uniform thickness laminated on the electrode can be obtained byapplyingpressure to the laminatedSPE composite electrodewith a force applied on the upper surface of the laminate and a force in opposition thereto applied on the lower surface of the laminate during the step of curing the adhesive, during the steps before the start of curing to the end of the curing, or after curing.
  • This method is particularly preferred as a method for laminating a SPE film and a method for producing a SPE composite electrode.
  • another SPE composite electrode such as a two member-SPE composite can be produced by a succeeding method which comprises removing the base film from the SPE composite electrode, and then (or while removing the base film) , laminating another constituent structural member such as a second electrode on the exposed SPE surface.
  • a SPE composite electrode in which a SPE film of uniform thickness is laminated on the electrode can be obtained by applying pressure to the laminate with a force applied on the upper surface of the laminate and a force in opposition thereto applied on the lower surface of the laminate by means of a press or roll method in the step of laminating another constituent structural member on the SPE surface.
  • This method is particularly preferred as a method for laminating aSPE filmandamethodforproducing a SPE composite electrode.
  • the pressurization conditions can be determined in a similar way as described in the preparation of a composite film as described above.
  • the atmosphere under which each step is conducted is preferably a moisture controlled atmosphere.
  • a dry atmosphere such as dry air, dry nitrogen and dry argon, if necessary, is preferably used because SPE's, in general, often have a moisture-absorbing property, and is particularly preferably used when the surface of the fluid SPE or fluid SPE material layer is exposed to the atmosphere.
  • the temperature at which each step is conducted is not particularly limited, as long as the temperature does not adversely affect the properties of the SPE film, and normally room temperature is appropriate. However, in the step of polymerizing a polymerizable compound by heat polymerization, heating is provided to the extent necessary to cause the polymerization reaction.
  • the water content was measured according to Karl Fischer's method.
  • the film thickness was measured using a dial thickness meter manufactured by Peacock.
  • the fluid SPE used herein was prepared by adding 1.5 parts by weight of Irgacure 500 (produced by Ciba Geigy AG, a polymerization initiator) to 100 parts by weight of a mixture consisting of 30 wt% of the following polyfunctional compound:
  • PET-1 polyester film (PET) (thickness: 12 ⁇ m)
  • ONy biaxially stretched nylon (-6,6) film
  • PET-2:PET-1 evaporated with alumina (thickness: 1,000A)
  • PET-3:PET-1 evaporated with silica (thickness:1,000A)
  • PET-4:PET-1 evaporated with aluminum (thickness:2,000A )
  • the cover film used herein was a 50 ⁇ m-thick biaxially stretched polypropylene film (hereinafter referred to as "OPP") or high density polyethylene film (hereinafter referred to as "PE” ) .
  • OPP biaxially stretched polypropylene film
  • PE high density polyethylene film
  • the electrode used herein was obtained by coating lithium cobaltate to a thickness of 70 ⁇ m on a 50 ⁇ m-thick aluminum foil.
  • the fluid SPE was coatedon PET-1 bymeans of a coaterusing a doctor knife method under an atmosphere having a dew point of -50 °C to a small thickness. Then, after irradiating with ultraviolet rays under a nitrogen atmosphere to polymerize and cross-link the polymerizable compound (the above polyfunctional compound) , OPP was laminated on the cured surface by means of nip rolls.
  • the laminate (composite film) comprising a SPE film layer
  • the ion conductivity of the SPE film of the composite film was 2 x 10 "3 S/cm when measured at 25 °C by a known AC impedance method.
  • a coated surface of an electrode on which the above fluid SPE was coated was laminated on the SPE surface of the laminate (composite film) obtained above by means of nip rolls while peeling off the cover film from the composite film.
  • Ultraviolet rays were irradiated through the PET film to polymerize (cross-link) the electrode coating and bond the electrode to the SPE to obtain a laminate (SPE composite electrode) by winding at a temperature of 20 °C and a humidity of 5 RH%.
  • the laminate (SPE composite electrode) thus obtained had a thin and uniform SPE film having a thickness of 50 ⁇ m ⁇ 20%.
  • the releasability of the PET film was good and the film could be peeled off without deforming the SPE film surface.
  • the water content of the SPE film was 200 ppm or less.
  • EXAMPLE 2 A SPE film (composite film) and SPE composite electrodewere obtained in the same manner as in Example 1, except for changing the base film to ONy.
  • the SPE film of the SPE composite electrode thus obtained had a thickness, thickness distribution, releasability and water content equal to the results obtained in Example 1.
  • a SPE film (composite film) and SPE composite electrode were obtained in the same manner as in Example 1, except that the base film was changed to PET-2 and an OPP cover film was not used.
  • SPE film of the SPE composite electrode thus obtained had a thickness of 30 ⁇ m ⁇ 10% and excellent uniformity.
  • the releasability of the PET film was very good and the film could be easily peeled off.
  • the water content of the SPE film was 500 ppm or less.
  • a SPE film (composite film) and SPE composite electrode were obtained in the same manner as in Example 1, except that the base film was changed to PET-3 and PE was used as the cover film.
  • the SPE film of the SPE composite electrode had a thickness of 30 ⁇ m ⁇ 20% and was uniform.
  • the releasability of the PET film and the water content of the SPE film were the same as in Example 1.
  • SPE film composite film
  • SPE composite electrode were obtained in the same manner as in Example 1, except that the base film was changed to PET-4.
  • the SPE film of the SPE composite electrode had a thickness, thickness distribution, releasability and water content equal to the results obtained in Example 4.
  • the resulting SPE composite electrode consisting of SPE/lithium cobaltate/aluminum foil was dipped in a IM LiBF 4 electrolytic solution (in diethylcarbonate/ethylene carbonate (1:1 in weight ratio)) for one hour. Then, the SPE surface of the SPE composite electrode was laminated on the lithium surface of a lithium foil having a copper foil previously laminated thereon.
  • IM LiBF 4 electrolytic solution in diethylcarbonate/ethylene carbonate (1:1 in weight ratio
  • a secondary battery element consisting of a SPE composite electrode (copper/lithium/SPE/lithium cobaltate/aluminum) .
  • the edge portions of the element were sealed with an epoxy resin to obtain a secondary battery.
  • the battery was subjected to repeated charging/discharging at a working voltage of from 2.0 to 4.2 V and acurrent density of 0.3mA/cm 2 for 150 cycles, and it was found that the battery maintained 50 % or more of its initial capacity.
  • An electrode was dipped in a fluid SPE under an atmosphere having a dewpoint of -50°C, excess fluidwas removedby nip rolls, the solution was coated as thin as possible by a coater in a doctor knife system, ultraviolet rays were irradiated thereon under a nitrogen atmosphere to polymerize (cross-link) the SPE, and a laminate was roll-winded under an atmosphere at a temperature of 20 °C and a humidity of 5 RH%. Although the coating was made as thin as possible, the thickness and distribution thereof were at least 200 ⁇ m ⁇ 20%. Thewatercontent of the SPEfilmof thelaminate immediately after winding was 1,000 ppm.
  • a SPE can easily be formed into a composite film, and handling after film formation is relatively easy.
  • the inventive method is useful as an industrial method for making batteries.
  • a SPE film having a large area can be continuously produced as a composite film in a simple and easy manner.
  • a SPE film of homogeneous ion conductivity and uniform thickness can be handled in a stable condition, and can be stably preserved. Furthermore, by using a composite film of the present invention, a SPE composite electrode can be obtained in which a SPE layer of homogeneous ion conductivity and uniform thickness is laminated on an electrode and in good electrical contact therewith. That is, in accordance with the invention, the SPE layer is homogeneously adhered to an electrode.
  • a SPE composite electrode having a large area in which a SPE layer of homogeneous ion conductivity and uniform thickness is laminated on an electrode in a homogeneously adhered state.
  • the present invention is extremely advantageous in producing a large numberof electrochemicalapparatus ofhomogeneous quality.
  • the step of forming a SPE film layer on an electrode can be simple and easy. This is because very strict moisture control of the atmosphere may not be necessary.

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  • Electrochemistry (AREA)
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  • Dispersion Chemistry (AREA)
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Abstract

La présente invention concerne un procédé de stratification d'un film électrolyte polymère solide consistant à stratifier une couche d'électrolyte polymère solide fluide sur un film de base ou sur une couche fine comprenant un métal ou un oxyde de métal qui est stratifié sur le film de base. Le procédé peut également consister à stratifier une couche d'électrolyte polymère solide fluide contenant un composé polymérisable, à polymériser le composé considéré, ce qui donne une couche d'électrolyte polymère solide sensiblement non fluable, puis à soumettre à une pression le stratifié résultant. Le procédé peut aussi consister à stratifier une couche d'électrolyte polymère solide fluide, puis à stratifier sur l'une de ses faces un film de couverture. Le procédé peut enfin consister à stratifier un électrolyte polymère solide fluide contenant un composé polymérisable, puis à polymériser le composé considéré. L'invention concerne également un procédé de production d'une électrode composite à électrolyte polymère solide en utilisant le film électrolyte polymère solide.
PCT/JP1997/000945 1996-03-21 1997-03-21 Procede de stratification d'un film electrolyte polymere solide WO1997035350A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US08/946,882 US5972054A (en) 1996-03-21 1997-10-08 Method for laminating solid polymer electrolyte film

Applications Claiming Priority (2)

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JP8/93681 1996-03-21
JP9368196 1996-03-21

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1560019A1 (fr) * 2004-01-28 2005-08-03 Mettler-Toledo GmbH Electrolyte polymère, demi-cellule pour des mesures électrochimiques et son utilisation
WO2008023835A1 (fr) * 2006-08-25 2008-02-28 Sumitomo Chemical Company, Limited Membrane électrolyte polymère, laminé de celle-ci, et leurs procédés de production

Citations (5)

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Publication number Priority date Publication date Assignee Title
US4935317A (en) * 1989-06-21 1990-06-19 Mhb Joint Venture Method for producing solid state electrochemical laminar cell utilizing cathode rolling step
US5376210A (en) * 1994-03-23 1994-12-27 Hydro-Quebec Peeling aids for LPB electrolytes and method of use
CA2123459A1 (fr) * 1994-03-23 1995-09-24 Guy St-Amant Procede pour l'assemblage des piles acep
US5470357A (en) * 1993-03-05 1995-11-28 Bell Communications Research, Inc. Method of making a laminated lithium-ion rechargeable battery cell
US5498489A (en) * 1995-04-14 1996-03-12 Dasgupta; Sankar Rechargeable non-aqueous lithium battery having stacked electrochemical cells

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4935317A (en) * 1989-06-21 1990-06-19 Mhb Joint Venture Method for producing solid state electrochemical laminar cell utilizing cathode rolling step
US5470357A (en) * 1993-03-05 1995-11-28 Bell Communications Research, Inc. Method of making a laminated lithium-ion rechargeable battery cell
US5376210A (en) * 1994-03-23 1994-12-27 Hydro-Quebec Peeling aids for LPB electrolytes and method of use
CA2123459A1 (fr) * 1994-03-23 1995-09-24 Guy St-Amant Procede pour l'assemblage des piles acep
US5536278A (en) * 1994-03-23 1996-07-16 Hydro-Quebec Process for assembling LPB batteries
US5498489A (en) * 1995-04-14 1996-03-12 Dasgupta; Sankar Rechargeable non-aqueous lithium battery having stacked electrochemical cells

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1560019A1 (fr) * 2004-01-28 2005-08-03 Mettler-Toledo GmbH Electrolyte polymère, demi-cellule pour des mesures électrochimiques et son utilisation
WO2005073704A1 (fr) * 2004-01-28 2005-08-11 Mettler-Toledo Gmbh Electrolyte polymere, demi-cellule pour mesures electrochimiques, et leur utilisation
US7790323B2 (en) 2004-01-28 2010-09-07 Mettler-Toledo Ag Polymer electrolyte, half-cell for electrochemical measurements, as well as the use thereof
WO2008023835A1 (fr) * 2006-08-25 2008-02-28 Sumitomo Chemical Company, Limited Membrane électrolyte polymère, laminé de celle-ci, et leurs procédés de production
EP2063478A1 (fr) * 2006-08-25 2009-05-27 Sumitomo Chemical Company, Limited Membrane électrolyte polymère, laminé de celle-ci, et leurs procédés de production
EP2063478A4 (fr) * 2006-08-25 2010-08-04 Sumitomo Chemical Co Membrane électrolyte polymère, laminé de celle-ci, et leurs procédés de production
EP2360762A1 (fr) * 2006-08-25 2011-08-24 Sumitomo Chemical Co., Ltd. Membrane électrolyte en polymère, son stratifié et leurs procédés de production

Also Published As

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