CA1309456C - Solid electrochemical element and production process thereof - Google Patents
Solid electrochemical element and production process thereofInfo
- Publication number
- CA1309456C CA1309456C CA 546422 CA546422A CA1309456C CA 1309456 C CA1309456 C CA 1309456C CA 546422 CA546422 CA 546422 CA 546422 A CA546422 A CA 546422A CA 1309456 C CA1309456 C CA 1309456C
- Authority
- CA
- Canada
- Prior art keywords
- solid electrolyte
- solid
- particles
- electrochemical element
- plastic resin
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
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Classifications
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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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
- H01M12/00—Hybrid cells; Manufacture thereof
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/188—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02E60/13—Energy storage using capacitors
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23—Sheet including cover or casing
- Y10T428/239—Complete cover or casing
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- 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
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
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- 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
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/2933—Coated or with bond, impregnation or core
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- 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
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
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- 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
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- Y10T428/31913—Monoolefin polymer
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Abstract
ABSTRACT
This invention provides a solid electrochemical element which has high flexibility and good environmental resistance and accordingly is superior to conventional solid electrochemical elements by using (a) solid electrolyte particles surrounded by a plastic resin and (b) electrode material particles surrounded or not surrounded by the plastic resin, as well as a process for producing said solid electrochemical element which uses, as starting materials, (a) solid electrolyte particles coated with a thin layer of a plastic resin and (b) electrode material particles coated with a thin layer of the plastic resin and which includes a step of crushing the solid electrolyte particles by pressing.
This invention provides a solid electrochemical element which has high flexibility and good environmental resistance and accordingly is superior to conventional solid electrochemical elements by using (a) solid electrolyte particles surrounded by a plastic resin and (b) electrode material particles surrounded or not surrounded by the plastic resin, as well as a process for producing said solid electrochemical element which uses, as starting materials, (a) solid electrolyte particles coated with a thin layer of a plastic resin and (b) electrode material particles coated with a thin layer of the plastic resin and which includes a step of crushing the solid electrolyte particles by pressing.
Description
1309~S6 ~ . pxes~-ult lnvelltioll rolate~ solid elect~.och~mical el.amerlts. More particu].ally, the present invention r~lates to such elements whicl) use an ion conductor and the consti-tuellt members o~ which arc ;111 solid, such as a solid c~ soli~ al~crical doubl~ .lay(~l ~apnc.Ltor, a 901id electroch~o~ic display or the like, as w~ll as to a proces~
~or produci~lg said ~lement.
I~ore pa~ticularly, tlle presen~ invelltion relates to a solid electrochelnical element witll (~xcellent mechani-cal strengtll and e:;cellent environmental resistance which is cônstituted by (a) an ionic conductor containing an insulatincJ ~.upportillc3 substance for soli,l electrolyte such a~s a plasti.c resill or the like and havill~l Elexibility and excellent environmental resistance and (1,) electrode material particles, as well as to a process Eor producing said elernent.
Solid electrochemical elements whose constituent members are all solid are advantageous in that tlley have no problem oE liquid leakage and that they can be easily produced in a small and thin sllape. In constituting such an element, there is required a solid ion conductor or moving ions witllill the element, namely, a solid electrolyte, The solid electrolyte is classified by the type of a movable lon and includes Li~-conductive solid electrolyte, Ag~-conductive solid electrolyte, Cu~-conductive solid electrolyte, H~-conductive solid ,,,~
`
~, 13094~6 1 electrolyte, etc. A sol~d electrochemical element is constituted by combining one oE these solid electrolytes with an appropriate electrode material.
Not only solid electrolytes but also general electrolytes have no dieectional property or no anisotropy with respect to the ion conductivity and accordingly have a random ion conductivity. Therefore, a solid electro-chemical element is ordinarily constituted by shaping a solid electrolyte powder into a layer by pressing or into a thin film by vapor deposition and providing a pair of electrodes on the both surfaces of the layer or the thin film to form one solid electrochemical element per one solid electrolyte layer.
In ordinary electrochemical elements using a liquid electrolyte, the electronic and ionic contact between electrolyte and electrode material can be easily obtained. In contrast, in solid electrochemical elements constituted by solid substances, generally it is not easy to obtain electronic and ionic contact between solid electrolytes, between electrode materials or between solid electrolyte and electrode material. In electrochemical elements using a liquid electrolyte, it is usual to add a foreign matter such as a binder or the like to the electrolyte or the electrode in order to prevent the leakage of the electrolyte or to prevent the excessive penetration of the electrolyte into the electrode and the resulting deformation of the electrode. Meanwhile in solid electrochemical elements, the addition of a foreign 13094~6 1 matter is ordinarily avoided because it reduces said electronic and ionic contact.
Using no foreign matter, the solid electrochemi-cal elements, when produced in a large and thin shape, generally tend to lack in elasticity and consequently are fragile to mechanical impacts and easily destroyed or impaired.
Further in the solid electrochemical elements, the solid electrolyte generally comprises a chemically active monovalent cation as a conducting element. This monovalent cation, when exposed to oxygen or moisture in the atmosphere, is converted to a divalent cation by oxidation or immobili2ed in the electrolyte crystal as an oxide, whereby the conducting function of the electrolyte is lost.
Furthermore, when a plurality of solid electro-chemical elements are arranged into an element group wherein they are connected in series or in parallel, it is necessary to isolate each constituent element of the element group electronically and ionically. In this case, since the electrolyte used in each element generally has random ion conductivity and has no anisotropy, each element must have an electrolyte layer ionically isolated from other electrolyte layers. Without this isolation, the ionic flow within the electrolyte of one element not only occurs between the electrodes of the element but also spreads into between the electrodes of other elements, whereby the element group fails to exhibit its desired `--``` 13094S6 function. This i5 a problem when a solid electrochemical element is produced in a small or miniature size, whi¢h i5 a feature of solid electrochemical elements, in addition to the above-mentioned problem when a solid electrochemical element is produced in a large and thin shape. The isolatlon of each element in an element group requires complicated assembly steps including photolithography, etc. as used in an ordinary semiconductor assembly line.
According to one aspect of this invention there is provided a solid electrochemical element which is flexible, has improved mechanical strength, and has improved stability upon exposure to the environment, comprising: at least one solid electrolyte sheet which is flexible, has a pair of opposing æurfaces, and is comprised of solid electrolyte , ~
particles and a plastic resin, which plastic resin was coated on each particle of said solid electrolyte particles prior to formation of said at least one solid electrolyte sheet; and at least two electrode sheets comprised of an electrode material, one of said at least two electrode sheets being ~oined to each of said pair of opposing surfaces of said at least one solid electrolyte sheet, wherein the at least one solid electrolyte sheet has a thickness and the solid - electrolyte particles have a particle diameter which does not exceed the thickness of the at least one solid electrolyte sheet.
. ~
-" 1309456 Aacording to another a~p~at o~ thi~ invention there i8 provided a process for producing a solid electrochemical element which is flexible, has improved mechanical strength and has improved stability upon exposure to the environment, the process comprising: a. separately dispersing electrode material particles and solid electrolyte particles in solvent containing a plastic resin dissolved therein to provide respective dispersions; b. evaporating solvent from each respective dispersion of step a to form powdery particles, their aggregates or their moldings, consisting of particles coated with plastic resin: c. forming at least one solid electrolyte sheet and at least two electrode sheets from the powdery particles, their aggregates or their moldings, respectively comprised of solid electrolyte particles coated with plastic resin and electrode material particles coated with plastic resin, wherein said at least one solid electrolyte sheet is flexible, has a pair of opposing surfaces, and has a thickness, wherein the solid electrolyte particles have a particle diameter which does not exceed the thickness of the at least one solid electrolyte sheet, and wherein said at least two electrode sheets are flexible; and d. joining one of the at least two electrode sheets to each pair of opposing surfaces of the at least one solid electrolyte sheet to form the solid electrochemical element.
According to another aspect of this invention there is provided a process for producing a solid electrochemical -` 1309456 element which is ~lexible, has improved mechanical strength and has improved stability upon exposure to the environment, the process comprising: a. separately mixing solid electrolyte particles and electrode material particles with plastic resin powder to provide respective mixtures; b.
separately forming using heat at least one solid electrolyte sheet and at least two electrode sheets from the respective mixtures of step a respectively comprised of solid electrolyte particles and plastic resin powder, and electrode material particles and plastic resin powder, wherein said at least one electrolyte sheet is flexible, has a pair of opposing surfaces, and has a thickness, wherein the solid electrolyte particles have a particle diameter which does not exceed the thickness of the at least one solid electrolyte sheet, and wherein said at least two electrode sheets are flexible; and c. joining one of the at least two electrode sheets to each of the pair of opposing surfaces of the at least one solid electrolyte sheet to from the solid electrochemical element.
According to the preferred embodiment of the present invention, there is provided a flexible, environment-resistant ion conductor by constituting it with a solid electrolyte and an insulating supporting substance for solid electrolyte surrounding the solid - 5a -1309~56 electrolyte, pre~erably with a solid electrolyte and a plastic ~ubstance. Preferably, an ion conduc~or i5 provided which has an anisotropic ion conductivity by allowing the plastic resin to have a thickness approximatley same as the particle diameter of the solid electrolyte particles or by alternately stacking in layers a sheet of a solid electrolyte and a sheet of a supporting substance for solid electrolyte such as a plas~ic resin or the like and cutting the resulting laminate in the thickness direction.
Such an ion conductor may be produced by a process including a step of crushing solid electrolyte particles by pressing. Preferably, solid electrolyte particles and a plastic resin powder or grain are mixed in a solvent or under heating and the mixture or its melt is shaped by rolling to obtain an ion conductor.
A solid electrochemical element may be provided with a flexibility and environmental resistance by surrounding solid electrolyte particles and electrode material particles with a plastic resin.
The solid electrochemical element may be produced by separately or jointly mixing solid electrolyte particles and electrode material particles with a plastic resin in a solvent or mixing these particles directly with a plastic resin powder or grain to obtain the particles coated with said plastic resin, shaping these coated particles to produce a shaped material of solid electrolyte particles and a shaped 13094~6 electrode material, and shaping these two materials into one integral body. Pxeferably, the solid electrochemical element is produced by a process including a step of crushing solid electrolyte particles by pressing.
Reference is now made to the accompanying drawings in which: -Fig. 1 is a schematic view showing the structure ofan embodiment of the ion conductor of the present invention.
Fig. 2 is a view showing steps of producing an ion conductor according to the present invention.
Fig. 3 is a view showing the structure of an ion conductor having an anisotropy with respect to the ion conductivity which is obtained by stacking in layers a solid electrolyte sheet and a sheet of a supporting substance for solid electrolyte such as a plastic resin or the like and then cutting the resulting laminate.
Fig. 4 is â view showing the structure of a laminated film battery using an ion conductor.
In Fig. 1, solid electrolyte particles 1 are surrounded by a supporting substance 2 for solid electrolyte, except for the upper and lower surfaces which are necessary for formation of an ion-conductive path.
A mixture 4 consisting of solid electrolyte partic]es, a suporting substance for solid electrolyte and a solvent is printed on a substrate 3 with a spatula 6, dried - 6a -1309~6 and then rolled by rollers 7 and 8, whereby an ion conductor is produced.
In conventional ion conductors consisting of a solid electrolyte or conventional solid electrochemical elements using a solid electrolyte, the use of a foreign substance has been avoided usually. However, in the ion conductor or solid electrochemical elemen~ of the present invention, there is used a foreign substance, namely, an insulating material which supports and surrounds a solid electrolyte. That is, the solid electrolyte material or the electrode material is surrounded by an insulating supporting material for solid electrolyte, preferably a plastic resin material, except for t.he portions which form an ion- or electron-conductive path optionally having a particular directionality. Accordingly, the insulating supporting substance for solid electrolyte is pushed into the gaps between the solid electrolyte particles or between the electrodP material particles in forming an ion - 6b -13094S~
1 conductor (a shaped material o~ solid electrolyte) or a shaped electrode material or in assembllng a solid electrochemical element, whereby an aggregate of particles is formed in which the neighbouring particles are in direct contact with one another and each particle i9 surrounded by the insulating supporting substance for solid electrolyte. As a result, the particles as a constituent member of the ion conductor, the electrode or the solid electrochemical element can keep a shape as an aggregate, can secure an electrical and ionic contact, and are not directly exposed to oxygen and moisture in the air and become unlikely to undergo deterioration.
These merits can be obtained more effectively by employing a step of crushing the solid electrolyte particles by pressing, in a process for producing an ion conductor (a shaped material of solid electrolyte), a shaped electrode material or a solid electrochemical element. When the solid electrolyte particles coated with a plastic resin (an insulating supporting substance for solid electrolyte) is crushed by pressing, there appear the surfaces thereof not coated with the plastic resin and, through these surfaces, there occur a direct contact between the solid electrolyte particles or between these particles and electrode particles. Thus, there can be obtained a sheet type ion conductor (a shaped material of solid electrolyte) with flexibility and excellent ion conductivity, as well as a shaped electrode material, and as a result there can be obtained a solid electrochemical 13094~6 1 element having an exc~llent mechanical strength and an excellent ~nvironmental resistance and capable of generating a large current.
The ion conductor of the present invention can also be formed in a sheet shape wherein surfaces of solid electrolyte particles are coated with an insulating supporting substance for solid electrolyte (e.g. a plastic resin) except for the particular surfaces, for example, the upper and lower surfaces. When two or more pairs of electrodes are provided on the upper and lower surfaces of the ion conductor, the electrodes cover and are contacted with the upper and lower portions of the solid electrolyte particles not coated with the insulating supporting substance, and thus the electrodes and the ion conductor are connected ionically. Within the ion conductor sheet, the ion does not move in the lateral direction but only in the vertical direction of the sheet, whereby no ionic flow occurs between the two neighbouring electrodes or between the two neighbouring but opposing electrodes. Thus, it is possible to constitute, using only one ion conductor sheet, a solid electrochemical element group consisting of a plurality of solid electrochemical elements which are electrically independent from one another, by providing two or more pairs of opposing electrodes on the two opposing surfaces of an ion conductor sheet.
In the present invention there is used an ion conductor consisting of solid electrolyte particles coated with an insulating supporting substance for solid ~3~g4~6 1 electrolyte, When this lon conductor is used in a solid electrochemical element, the upper and lower surfaces of the ion conductor are provided with electrodes. There-fore, the ion conductor may be produced in such a manner that the upper and lower surface on which electrodes are to be provided, may be coated very thinly or may not be coated substantially with an insulating supporting substance for solid electrolyte in order to obtain a good ionic contact between the ion conductor and the electrodes.
The insulating supporting substance for solid electrolyte according to the present invention can be any substance as long as it can surround solid electrolyte particles and can form a flexible aggregate of the solid electrolyte particles. Particularly, a plastic resin is preferred. As the plastic resin, there can be preferably used those which can be stably mixed with a solid electrolyte containing a high concentration of a chemi-cally active monovalent cation such as Na+, Li+, Ag+, Cu+, H+ or the like or with an electrode material as a strong oxidizing agent or a strong reducing agent. Such plastic resins are, for example, polyethylene, polypro-pylene, synthetic rubbers (e.g., styrene-butadlene rubber, Neoprene rubber), silicone resins, acrylic resins, etc.
When a polyethylene, polypropylene or acrylic resin is used, the fine powder of the resin is dry-blended with a solid electrolyte powder or grain or with an electrode material powder or grain. The particle diameter of the resin is preferably 1/10 to 1/10,000 time the _ g _ 1 particle diameter of each powder or grain. During the blendin~, the particles of the polyethylene, polypropylene or acrylic resin coat the surface of each particle of the powers or grains owing to the static electricity generated between the particles.
When a synthetic rubber such as styrene-butadiene rubber, Neoprene rubber or the like, a silicone resin or an acrylic resin is used, wet blending is conducted using an organic solvent such as toluene, xylene or the like.
That is, a synthetic rubber, an acrylic resin or a silicone resin is dissolved in an organic solvent in an amount of 5 to 20% by weight; to the solution is added a solid electrolyte powder or grain or an electrode material powder or grain; they are mixed and dispersed to obtain a ~a ~o~n~o~k~
fi~ slurry the slurry is casted on a Teflonlsheet; and the solvent is removed under vacuum, if necessary with heat-ing, whereby a shaped body can be obtained. Alterna-tively, the slurry itself can be treated under vaccum to remove the solvent and then shaped by pressing.
The solid electrolyte used in the present inven-tion includes Li+-conductive solid electrolytes such as LiI, LiI H2O, Li3N, Li4Sio4-Li3-Li3PO4, p Y
oxide-LiCF3SO3 and the like; Ag+-conductive solid electrolytes such as RbAg4I5, Ag3SI, AgI-Ag2O-MoO3 glass and the like; Cu+-conductive solid electrolytes such as RbCu I 5C13 5, RbCu4I1 25C13 75~ K0.2R 0.8 4 1.5 3.5 CuI-Cu2O-MoO3 glass and the like; H+-conductive solid 13094~6 1 electrolyteS such as H3Mol2P40 29H2~ 3 12 40 2 the like; and Na+-conductive solid electrolytes represent-ed by Na-~-A1203 (sodium ~-alumina) or Nal+xZr2P3 xSix012 ~0 ~ x ~ 3).
As the electrode material of the present inven-tion, there can be used, for example, carbon materials such as graphite, acetylene black, active carbon and the like: sulfides such as titanium sulfide, niobium sulfide, cuprous sulfide, silver sulfide, lead sulfide, iron sulfide and the like; oxides such as tungsten oxide, vanadium oxide, chromium oxide, molybdenum oxide, titanium oxide, iron oxide, silver oxide, copper oxide and the like; halides such as silver chloride, lead iodide, cuprous iodide and the like; and metal materials such as copper, silver, lithium, gold, platinum, titanium and their alloys.
A solid electrolyte cell or battery can be constituted by combining an ion conductor (a shaped material of solid electrolyte particlesl and an electrode material which can give ion to the ion conductor or receive ion therefrom, such as titanium disulfide or the like.
A solid electrochemical display element (a solid electrochromic display) can be constituted by using an ion conductor and an electrode material which can give or receive ion and simultaneosuly causes an optical change, such as tungsten oxide or the like.
A solid electrical double layer capacitor can be ~3094~6 1 constituted by using an ton conductor and an electrode material which does not glve or receive ion but can form an electrical double layer at the interface with the ion conductor, such as active carbon or the like.
All of these solid electrochemical elements according to the present invention have a sufficient flxibility, an excellent mechanical strength and an excellent environmental resistance.
A solid electrolyte, for example, a powder of RbCu4I1 5C13 5 of 200 mesh pass through 100% is dispersed in a toluene solution of a styrene-butadiene copolymer so that the volume fraction of the powder after drying becomes 85~. The resulting slurry is spread on a Teflon sheet using an applicator bar and they are placed in dry air to remove toluene, whereby a flexible sheet type ion conductor (a shaped material of solid electrolyte particles) having no fluidity is obtained. This ion conductor can be used as it is for constitution of a solid electrochemical element but, by rolling it with a roller press so as to have a thickness of about 2/3 or less of the original thickness, can be made into a sheet type ion conductor with improved ion conductivity wherein the solid electrolyte particles have been crushed by pressing.
A shaped electrode material can also be formed in a similar manner. In forming a shaped electrode material using, for example, copper as an electrode material, a copper powder having particle diameters of 5 microns or less and a RbCu4I1 5C13 5 powder having 13094~6 1 particle diameters of 200 me~h pass through 100% are mixed at a weight ratio of 90 : 10. The mixed powder is dispersed in a toluene solution of a styrene-butadiene copolymer so that the volume fraction of the mixed powder after drying becomes 90~. The resulting slurry is spread on a Teflon sheet using an applicator bar and they are placed in dry air to remove toluene, whereby a flexible sheet type shaped electrode ma~erial is obtained. It can be rolled by a roller press to have a thickness of about 2/3 or less of the original thickness, whereby an elec-trode having an excellent electrical conductivity and an excellent ionic conductivity can be obtained.
By press-molding the ion conductor interposed between the shaped electrode materials thus obtained together with, if necessary, other constituent members such as a current collector into one integral body, a solid electrochemical element can be obtained.
Production of a solid electrochemical element - can be conducted as above by making a shaped ion conductor and a shaped electrode material into one integral body.
Alternatively, it can be conducted by directly shaping the respective powders or grains coated with a plastic resin into one integral body.
The present invention will be described in detail below by way of Examples and Comparative Examples.
Example 1 Fig. 1 shows the structure of an ion conductor 13094~6 1 according to the present invention. Fig. l~a) is a plane view of the ion conductor and Fig. l(b) i~ a sectional view obtained by cutting the ion conductor of Fig. l(a) at a line C. In Figs. l(a) and l(b), 1 is a particulate solid electrolyte and 2 is an insulating supporting substance ~or solid electrolyte. The slant line portions are the portions of the particulate solid electrolyte hidden by the insulating supporting substance for solid electrolyte. RbCu4I1 5C13 5 as a particulate solid elec-trolyte was ground with a ball mill under dry air, andonly the solid electrolyte having particle diameters of 80 to 100 microns was used by sieving. A silicone rubber was used as a supporting substance for solid electrolyte.
Preparation of an ion conductor was conducted according to Fig. 2. Firstly, the above two materials were mixed at a ratio of 1 : 1 by weight. Mixing was conducted thoroughly using toluene as a solvent in order to sufficiently disperse the particulate solid electrolyte in the silicone rubber. The resulting mixture 4 was screen-printed on a stainless steel substrate 3 with a spatula 6 using a stainless steel screen 5 of 100 mesh through [see Fig.
2(a)]. Then, toluene was vaporized [see Fig. 2(b)].
Subsequently, the particulate solid electrolyte supported by the silicone rubber was rolled together with a silicone rubber 9 between two rollers 7 and 8 whose gaps had been adjusted to 100 microns to obtain an ion conductor sheet having a thickness of 100 microns [see Fig. 2(c)]. This ion conductor sheet showed an anisotropy with respect to 1~094~6 1 the ion conductivity. The ion conductivity at 25C was 4.5 x 10 2 n lcm 1 in the thickness direction and 7.3 x 10 12 Q lcm 1 in the lateral direction.
Examples 2 to 4 S Vsing other particulate solid electrolytes and supporting substances for solid electrolyte, ion con-ductors were prepared in the same manner as in Example 1.
Each ion conductor showed an anisotropy with respect to the ion conductivity. The results are shown in Table 1.
C l l l o o o o ~-V , , , ~ t, X X X
.~ ~J ~ D
.~ ~ ~ ~ ~ ~
Ul _ C~O ~C l l l o I ~g o o o o C~ C~ V ,, , ,, o o ~ X X
H S -~ 1~'1 t~l OD
E-l~ ~D ~` I_ C C C
~ ~> ~ ~
O O ~ O
ca E l 1:~ E~
a c a~ ~ ~ a~
aJ ~ I C Q) Q
~1 v c ,i O a Q Ll ~a O ~ C-,l sl a) ~ O ~_I
11~ o v u~ v a~ ~ a) Ll Q~ I~ ~
E-~ ~ IQ t> ~ a Q S2~ Q r~ Q
~Q Ll ~ :~1V 5:~ O .a ~I Q
:~ :J o _I v :~ ~ a) ~ .,~ :~
u~ 1 a) u~ Q ~-I Z ~-I tQ
~_ ~
C 0,~
V Ll ~ O
~ O .,1 ~O ~ ~
O .~ ~3 C 5 Ll V O O V O ~>
v ~ 0~ e o~ ~
a ~ P. o ~ o ~ ~ o o O
~ ~ r~ _i æ _i r~ ~ ~ ~ ~ _ o ~: o ~ ~ ~ er X
13094~6 1 Example 5 NASICON ~Na-super ion conductor), a Na -conduc-tive solid electrolyte represented by Nal+xZr2P3_xSixOl2 (0 ~ x ~ 3) was ground so as to have particle diameters of 100 ~ 10 microns, and these particles were used as a particulate solid electrolyte. A polyethylene powder having a particle diameter of 100 microns was used as a supporting substance for solid electrolyte. In order to prepare an ion conductor sheet, the particulate solid electrolyte and the polyethylene powder were mixed; the mixture was melted at 200C; and the melt was rolled between hot rollers whose gaps had been adjusted to 100 microns to obtain a sheet. The temperature of the hot rollers was set at 30C. The sheet had ion conductivities of 7.3 x 10 5 Q lcm 1 in the thickness direction and 2.6 x 10 13 Q lcm 1 in the lateral direction. By melting, the polyethylene could effectively surround each solid elec-trolyte particle.
Example 6 An ion conductor sheet was prepared in the same manner as in Example 5 except that the polyethylene as a supporting substance for solid electrolyte was changed to a polypropylene resin. The sheet had ion conductivities of 5.4 x 10 5 Q lcm 1 in the thickness direction and ~.1 x 10 13 Q lcm 1 in the lateral direction.
-13~94~6 1 Example 7 Another embodlment of the ion conductor accord-ing to the present invention is shown in Fig. 3. A sheet 10 of a polyethylene oxide (PE0)-LiCF3S03 polymer elec-trolyte having a thickness of 100 microns was used as asolid electrolyte. The sheet was prepared by mlxing LiCF3S03 and a PE0 having a molecular weight of 750,000, dissolving the mixture in acetonitrile, casting the solution on a stainless steel plate, and vaporizing the solvent at 70C. Separately, a sheet 11 of the PE0 alone was prepared in a similar manner. The two sheets were stacked alternately ~see Fig. 3(a)], and the laminate was cut at a line B to prepare a zebra-patterned sheet [see Fig. 3(b)]. The sheet was measured for ion conduc-tivities regarding the surfaces a, b and c. They were 3.4x 10 6 Q lcm 1 between the surfaces a and b and 7.1 x 10 13 Q lcm 1 between the surfaces b and c.
Example 8 An ion conductor sheet was prepared in the same manner as in Example 1 except that 60~ by weight of white insulating particles of TiO2 (70 microns in particle diameter) had been added to the silicone rubber of Example 1. The sheet had ion conductivities of 5.7 x 10 3 Q lcm 1 in the thickness direction and 2.2 x 10 13 Q lcm 1 in the lateral direction A laminate type thin film battery was prepared using an ion conductor prepared as above. The preparation ~o~
1 process is shown in Fig. 4. The positive electrode group of the battery is shown in Fig, 4~a) and the negative electrode group is shown in Fig. 4(b). The positive electrode group was prepared by vapor-depositing stainless steel on a glass substrate through a mask to form stain-less steel portions 13, 15 and 17 and then vapor-deposit-ing thereon CuI through a mask to form CuI portions 14 in a thickness of 3,000 ~ [see Fig. 4(a)]. The portions 15 and 17 later become a positive electrode terminal and a negative electrode terminal, respectively. In a similar manner, the negative electrode group was prepared by vapor-depositing stainless steel on a glass substrate 12 through a mask to form stainless steel portions 13 and then vapor-depositing thereon copper through a mask to ~orm copper portions 16 [see Fig. 4(b)]. The above mentioned ion conductor sheet consisting of a particulate solid electrolyte 1 and a supporting substance 2 for solid electrolyte was put between the positive electrode group and the negative electrode group so that the electrode groups faced each other, and the circumference of the resulting laminate was coated with an epoxy adhesive 18, whereby a battery was prepared [see Fig. 4(d)]. The connection of the electrode groups was conducted using indium metal 19. The resulting battery was measured for electromotive force, and a voltage of 1.8 V existed between the positive electrode terminal 15 and the negative electrode terminal 17. Since the electromotive force of this battery was 0.6 V per single cell, it was ~309~6 1 found that the use of an ion conductor sheet according to this invention makes it unnecessary to divlde the electrolyte into each single cell portion. Further, in order to examine an effect when a plastic supporting substance for solid electrolyte is used, a battery was constituted by using, as a substrate 12 for each electrode group, a polyimide film having a thickness of 0.4 mm. As a result, it was found that the battery had an excellent elasticity. Therefore, this battery was found to be suitable for use as an electric source for IC cards requiring an elasticity. It was further found that the ion conductor sheet containing insulating particles, prepared in Example 8, when put between transparent electrodes, produced a sharp pink color on a white back-ground due to the precipitation of copper when a voltage was applied between the transparent electrodes and accordingly is suitable for use as an electrolyte for electrochromic display.
Example 9 A powder of 5 microns or less as particulate solid electrolyte was sufficiently mixed with a toluene solution containing 10~ of a styrene-butadiene copolymer, in a volume ratio of 85 (solid electrolyte) to 15 (copolymer~. In mixing, a suitable amount of toluene was used as a diluent.
The mixture thus prepared was a slurry having slight fluidity. The slurry was extended on a Teflon 1309~6 1 sheet in a thickness of 100 microns using an applicator bar. Toluene was vap~rized ln dry air and then the dried ~ilm was rolled into a film thickness of 70 microns using a roller press to crush the solid electrolyte particles, whereby a desired ion conductor was obtained.
In order to measure the ion conductivity, the ion conductor was cut into specimen of 1 cm2. On the two surfaces of the specimen were provided two copper electrodes each having the same size as the specimen, in a sandwich form. This was done by wetting the ion conductor surfaces with toluene and then pressing the electrodes thereon. Subsequently, an AC having a voltage of 10 mV
and a frequency of 1 KHz was applied between the two electrodes and the resulting AC resistance was measured.
It was 1.5 x 10 4 S/cm2.
In a comparative test for examining the effect of crushing by pressing, an ion conductor sheet was prepared according to the following manner. As a particulate solid electrolyte, there was used a powder having particle diameters of 1 micron or less which was difficult to be crushed by rolling, and an ion conductor sheet was prepared in the same manner as in Example 9.
The resulting ion conductor showed a low ion conductivity of 9.5 x 10-6 S/cm2.
An ion conductor sheet was prepared in the same manner as in the sheet of Example 9 except that crushing and rolling was conducted using an ordinary press in place of the roller press. That is, the ion conductor sheet 1309~
1 before crushing and rolling was sandwiched be~ween two stainless steel plates (in the form of a square of 10 cm x 10 cm having a thickness of 1 cm); using spacers of 70 microns in thickness, a pressure of 1 ton/cm2 was applied by a press to crush the solid electrolyte particles. The resulting ion conductor sheet had an ion conductivity of 9.7 x 10-5 S/cm2.
The reason is not clear yet but roller pressing, as compared with ordinary pressing by a press, can crush solid electrolyte particles more effectively and can provided an ion conductor with superior ion conductivity.
Example 10 100 parts by weight of a solid electrolyte, namely, a powder of a Cu+-conductive solid electrolyte represented by RbCu4I1 5C13 5, having an average particle diameter of 10 microns was mixed with 20 parts by weight of a polyethylene powder having an average particle diameter of 0.1 micron in a dry nitrogen atmosphere. The mixture was formed into a shaped solid electrolyte material of 5 mm x 20 mm x 100 microns (thickness) using a roller press at a pressure of 200 kg/cm2. In a similar manner, there was obtained a shaped positive electrode material of 5 mm x 20 mm x 200 microns (thickness) consisting of 50 parts by weight of a powder of a positive electrode active substance represented by CuO lNbS2, having an average particle diameter of 15 microns, 50 parts by weight of the above mentioned solid electrolyte -" 1309456 1 powder and lS parts by weight of the above mentioned polyethylene powder. Also in a similar manner, there was obtained a shaped negative electrode material of 5 mm x 20 mm x 120 microns (thickness) consisting of 50 parts by weight of a powder of a negative electrode active substance tmetallic copper) having an average particle diameter of 8 microns, 50 parts by weight of the above mentioned solid electrolyte powder and 25 parts by weight of the above mentioned polyethylene powder. These shaped materials were stacked in three layers and a pressure of 250 kg/cm2 was applied thereto, whereby a copper type solid cell A was obtained as an integral body.
Example 11 A copper type solid cell B was obtained in the same manner as in Example 10 except that a polypropylene powder having an average particle diameter of 0.1 micron was used in place of the polyethylene powder.
Comparative Example 1 A copper type solid cell C was obtained in the same manner as in Example 10 except that no polyethylene powder was used.
Example 12 An Ag type solid cell D was obtained in the same manner as in Example 10 except that there were used, as a solid electrolyte, a powder of an Ag+-conductive solid 13094~6 1 electrolyte represented by ~bAg4I5, having an average particle diameter of 8 microns, as a positive electrode active substance, a powder of AgO lNbS2 having an average particle diameter of 15 microns, and as a negative elec-trode active substance, a powder of metallic silver havingan average particle diameter of 8 microns.
Comparative Example 2 An Ag type solid cell E was obtained in the same manner as in Example 12 except that no polyethylene powder was used.
Example 13 A Li type solid cell F was obtained in the same manner as in Example 10 except that there were used, as a solid electrolyte, a powder of a Li+-conductive solid electrolyte represented by LiI, having an average particle diameter of 15 microns, as a positive electrode active substance, a powder of WO3 having an average particle diameter of 12 microns, and as a negative electrode active substance, a powder of Lil 5WO3 having an average particle diameter of 10 microns.
Comparative Example 3 A Li type solid cell G was obtained in the same manner as in Example 13 except that no polyethylene powder was used.
1 Example 14 An H type solid cell H was obtained in the same manner as in Example 10 except that there were used, as a solid electrolyte, a powder of a H+-conductive solid S electrolyte represented by H3Mol2PO40 29H2O, having an average particle diameter of 20 microns, as a positive electrode active substance, a powder of WO3 having an average particle diameter of 8 microns, and as a negative electrode active substance, a powder of HWO3 having an average particle diameter of 8 microns, and the polyethy-lene powder was changed to an acrylic resin powder having an average particle diameter of 0.2 micron.
Comparative Example 4 An H type solid cell I was obtained in the same manner as in Example 14 except that no acrylic resin powder was used.
Example 15 100 parts by weight of a solid electrolyte, namely, a powder of a Cu+-conductive solid electrolyte represented by RbCu4I1 25C13 75, having an average particle diameter of 2 microns was mixed with 30 parts by weight of a toluene solution containing 10% by weight of a styrene-butadiene rubber to obtain a solid electrolyte slurry. The slurry was extended on a fluoresin plate using a bar coater in a thickness (when dried~ of 20 microns and then dried for 3 hours at 50C under a reduced 1309~56 1 pressure of 1 Torr, whereby a solid electrolyte thin film of 60 mm (width) x 800 mm ~length) x 20 microns (thick-ness) was obtained.
Separately, 50 parts by weight of a graphite powder having an average particle diameter of 0.5 micron and 50 parts by weight of the above mentioned solid electrolyte powder were mixed with 35 parts by weight of the above mentioned toluene solution to obtain a positive electrode slurry. In a similar manner and using this slurry, there was obtained a positive electrode thin film of 60 mm (width) x 800 mm (length) x 30 microns (thick-ness).
Separately, 50 parts by weight of a metallic copper powder having an average particle diameter of 2 microns, 50 parts by weight of the above mentioned solid electrolyte powder and 18 parts by weight of the above mentioned toluene solution were mixed to obtain a negative electrode slurry. In a similar manner and using this slurry, there was obtained a negative electrode thin film of 60 mm (width) x 800 mm (length) x 20 microns (thick-ness).
Then, the positive electrode thin film was provided on one surface of the solid electrolyte thin film and the negative electrode thin film was provided on the other surface of the solid electrolyte thin film. They were shaped into one integral body at a pressure of 20 kg/cm using a roller press of 130 to 150C to obtain a thin film of 65 mm (width) x 1,000 mm (length) x 55 to 65 13094~6 1 microns ~thickness). This thin film was cut into pieces of 5 mm x 20 mm to obtain a solid cell J.
Example 16 A solid cell K was obtained in the same manner as in Example 15 except that the styrene-butadiene rubber was changed to a silicone resin.
Example 17 A solid cell L was obtained in the same manner as in Example 15 except that the styrene-butadiene rubber was changed to an acrylic resin.
Example 18 on the two surfaces of a solid electrolyte film having a thickness of 20 microns, obtained in the same manner as in Example 15, were provided an electrode film having a thickness o~ 30 microns and consisting of a graphite powder, a solid electrolyte powder and a styrene-butadiene rubber, obtained in the same manner as in Example 15. They were shaped into one integral body at a pressure of 20 kg/cm2 and at 130 to 150C using a roller press to obtain a sheet of 65 mm (width) x 1,000 mm (length) x 60 to 65 microns (thickness). The sheet was cut into pieces of 5 mm x 20 mm to obtain a solid electri-cal double layer capacitor M.
13094~6 1 Example 19 50 parts by weight o~ a solid electrolyte, namely, a powder of a H+-conductive solid electrolyte y 3Mol2PO40 29H2O, having an average particle diameter of 20 microns, 20 parts by weight of an acrylic resin powder having an average particle diameter of 0.2 micron and a graphite powder having an average particle diameter of 0.5 micron were mixed and shaped in the same manner as in Example 10 to prepare a graphite 10 electrode of 5 mm x 20 mm x 30 microns (thickness). Three layers comprising in the following order (a) the above electrode, (b) a solid electrolyte film of 5 mm x 20 mm x 50 microns (thickness) consisting of a H+-conductive solid electrolyte and an acrylic resin and (c) a display 15 electrode of 5 mm x 20 mm x 10 microns (thickness) containing tungsten trioxide (WO3), prepared in the same manner as in Example 14 were pressed into one body, whereby a solid electrochromic display element N of 5 mm x 20 mm x 85 microns (thickness) was assembled.
The above prepared solid cells A to L, solid electrical double layer capacitor M and solid electro-chromic display element N were subjected to repeated bending test (30 bending in the longitudinal direction).
The number of times of bending until breakage occured in each test is shown in Table 2. Also shown in Table 2 is the ratio of RltRo of each of the elements A to N wherein : Rl is the internal resistance of an element when the element has been allowed to stand for 48 hours in an 13094~6 1 atmosphere of 45C and 60~ humldity and Ro is the initial internal resistance of the element.
All of the solid electrochemical elements A, B, D, F, H, J, K, L, M and N according to the present inven-tion can withstand bending of several hundred times to several thousand times, and any of them does not show a noticeable increase in the internal resistance, when allowed to stand in the atmosphere. Meanwhile, the solid electrochemical elements C, E, G and I for comparison have no flexibility at all and are broken in bending of only one time and, when allowed to stand in the atmosphere, show a significant increase in the internal resistance.
~"` ~3094~i6 n -- 3~ --
~or produci~lg said ~lement.
I~ore pa~ticularly, tlle presen~ invelltion relates to a solid electrochelnical element witll (~xcellent mechani-cal strengtll and e:;cellent environmental resistance which is cônstituted by (a) an ionic conductor containing an insulatincJ ~.upportillc3 substance for soli,l electrolyte such a~s a plasti.c resill or the like and havill~l Elexibility and excellent environmental resistance and (1,) electrode material particles, as well as to a process Eor producing said elernent.
Solid electrochemical elements whose constituent members are all solid are advantageous in that tlley have no problem oE liquid leakage and that they can be easily produced in a small and thin sllape. In constituting such an element, there is required a solid ion conductor or moving ions witllill the element, namely, a solid electrolyte, The solid electrolyte is classified by the type of a movable lon and includes Li~-conductive solid electrolyte, Ag~-conductive solid electrolyte, Cu~-conductive solid electrolyte, H~-conductive solid ,,,~
`
~, 13094~6 1 electrolyte, etc. A sol~d electrochemical element is constituted by combining one oE these solid electrolytes with an appropriate electrode material.
Not only solid electrolytes but also general electrolytes have no dieectional property or no anisotropy with respect to the ion conductivity and accordingly have a random ion conductivity. Therefore, a solid electro-chemical element is ordinarily constituted by shaping a solid electrolyte powder into a layer by pressing or into a thin film by vapor deposition and providing a pair of electrodes on the both surfaces of the layer or the thin film to form one solid electrochemical element per one solid electrolyte layer.
In ordinary electrochemical elements using a liquid electrolyte, the electronic and ionic contact between electrolyte and electrode material can be easily obtained. In contrast, in solid electrochemical elements constituted by solid substances, generally it is not easy to obtain electronic and ionic contact between solid electrolytes, between electrode materials or between solid electrolyte and electrode material. In electrochemical elements using a liquid electrolyte, it is usual to add a foreign matter such as a binder or the like to the electrolyte or the electrode in order to prevent the leakage of the electrolyte or to prevent the excessive penetration of the electrolyte into the electrode and the resulting deformation of the electrode. Meanwhile in solid electrochemical elements, the addition of a foreign 13094~6 1 matter is ordinarily avoided because it reduces said electronic and ionic contact.
Using no foreign matter, the solid electrochemi-cal elements, when produced in a large and thin shape, generally tend to lack in elasticity and consequently are fragile to mechanical impacts and easily destroyed or impaired.
Further in the solid electrochemical elements, the solid electrolyte generally comprises a chemically active monovalent cation as a conducting element. This monovalent cation, when exposed to oxygen or moisture in the atmosphere, is converted to a divalent cation by oxidation or immobili2ed in the electrolyte crystal as an oxide, whereby the conducting function of the electrolyte is lost.
Furthermore, when a plurality of solid electro-chemical elements are arranged into an element group wherein they are connected in series or in parallel, it is necessary to isolate each constituent element of the element group electronically and ionically. In this case, since the electrolyte used in each element generally has random ion conductivity and has no anisotropy, each element must have an electrolyte layer ionically isolated from other electrolyte layers. Without this isolation, the ionic flow within the electrolyte of one element not only occurs between the electrodes of the element but also spreads into between the electrodes of other elements, whereby the element group fails to exhibit its desired `--``` 13094S6 function. This i5 a problem when a solid electrochemical element is produced in a small or miniature size, whi¢h i5 a feature of solid electrochemical elements, in addition to the above-mentioned problem when a solid electrochemical element is produced in a large and thin shape. The isolatlon of each element in an element group requires complicated assembly steps including photolithography, etc. as used in an ordinary semiconductor assembly line.
According to one aspect of this invention there is provided a solid electrochemical element which is flexible, has improved mechanical strength, and has improved stability upon exposure to the environment, comprising: at least one solid electrolyte sheet which is flexible, has a pair of opposing æurfaces, and is comprised of solid electrolyte , ~
particles and a plastic resin, which plastic resin was coated on each particle of said solid electrolyte particles prior to formation of said at least one solid electrolyte sheet; and at least two electrode sheets comprised of an electrode material, one of said at least two electrode sheets being ~oined to each of said pair of opposing surfaces of said at least one solid electrolyte sheet, wherein the at least one solid electrolyte sheet has a thickness and the solid - electrolyte particles have a particle diameter which does not exceed the thickness of the at least one solid electrolyte sheet.
. ~
-" 1309456 Aacording to another a~p~at o~ thi~ invention there i8 provided a process for producing a solid electrochemical element which is flexible, has improved mechanical strength and has improved stability upon exposure to the environment, the process comprising: a. separately dispersing electrode material particles and solid electrolyte particles in solvent containing a plastic resin dissolved therein to provide respective dispersions; b. evaporating solvent from each respective dispersion of step a to form powdery particles, their aggregates or their moldings, consisting of particles coated with plastic resin: c. forming at least one solid electrolyte sheet and at least two electrode sheets from the powdery particles, their aggregates or their moldings, respectively comprised of solid electrolyte particles coated with plastic resin and electrode material particles coated with plastic resin, wherein said at least one solid electrolyte sheet is flexible, has a pair of opposing surfaces, and has a thickness, wherein the solid electrolyte particles have a particle diameter which does not exceed the thickness of the at least one solid electrolyte sheet, and wherein said at least two electrode sheets are flexible; and d. joining one of the at least two electrode sheets to each pair of opposing surfaces of the at least one solid electrolyte sheet to form the solid electrochemical element.
According to another aspect of this invention there is provided a process for producing a solid electrochemical -` 1309456 element which is ~lexible, has improved mechanical strength and has improved stability upon exposure to the environment, the process comprising: a. separately mixing solid electrolyte particles and electrode material particles with plastic resin powder to provide respective mixtures; b.
separately forming using heat at least one solid electrolyte sheet and at least two electrode sheets from the respective mixtures of step a respectively comprised of solid electrolyte particles and plastic resin powder, and electrode material particles and plastic resin powder, wherein said at least one electrolyte sheet is flexible, has a pair of opposing surfaces, and has a thickness, wherein the solid electrolyte particles have a particle diameter which does not exceed the thickness of the at least one solid electrolyte sheet, and wherein said at least two electrode sheets are flexible; and c. joining one of the at least two electrode sheets to each of the pair of opposing surfaces of the at least one solid electrolyte sheet to from the solid electrochemical element.
According to the preferred embodiment of the present invention, there is provided a flexible, environment-resistant ion conductor by constituting it with a solid electrolyte and an insulating supporting substance for solid electrolyte surrounding the solid - 5a -1309~56 electrolyte, pre~erably with a solid electrolyte and a plastic ~ubstance. Preferably, an ion conduc~or i5 provided which has an anisotropic ion conductivity by allowing the plastic resin to have a thickness approximatley same as the particle diameter of the solid electrolyte particles or by alternately stacking in layers a sheet of a solid electrolyte and a sheet of a supporting substance for solid electrolyte such as a plas~ic resin or the like and cutting the resulting laminate in the thickness direction.
Such an ion conductor may be produced by a process including a step of crushing solid electrolyte particles by pressing. Preferably, solid electrolyte particles and a plastic resin powder or grain are mixed in a solvent or under heating and the mixture or its melt is shaped by rolling to obtain an ion conductor.
A solid electrochemical element may be provided with a flexibility and environmental resistance by surrounding solid electrolyte particles and electrode material particles with a plastic resin.
The solid electrochemical element may be produced by separately or jointly mixing solid electrolyte particles and electrode material particles with a plastic resin in a solvent or mixing these particles directly with a plastic resin powder or grain to obtain the particles coated with said plastic resin, shaping these coated particles to produce a shaped material of solid electrolyte particles and a shaped 13094~6 electrode material, and shaping these two materials into one integral body. Pxeferably, the solid electrochemical element is produced by a process including a step of crushing solid electrolyte particles by pressing.
Reference is now made to the accompanying drawings in which: -Fig. 1 is a schematic view showing the structure ofan embodiment of the ion conductor of the present invention.
Fig. 2 is a view showing steps of producing an ion conductor according to the present invention.
Fig. 3 is a view showing the structure of an ion conductor having an anisotropy with respect to the ion conductivity which is obtained by stacking in layers a solid electrolyte sheet and a sheet of a supporting substance for solid electrolyte such as a plastic resin or the like and then cutting the resulting laminate.
Fig. 4 is â view showing the structure of a laminated film battery using an ion conductor.
In Fig. 1, solid electrolyte particles 1 are surrounded by a supporting substance 2 for solid electrolyte, except for the upper and lower surfaces which are necessary for formation of an ion-conductive path.
A mixture 4 consisting of solid electrolyte partic]es, a suporting substance for solid electrolyte and a solvent is printed on a substrate 3 with a spatula 6, dried - 6a -1309~6 and then rolled by rollers 7 and 8, whereby an ion conductor is produced.
In conventional ion conductors consisting of a solid electrolyte or conventional solid electrochemical elements using a solid electrolyte, the use of a foreign substance has been avoided usually. However, in the ion conductor or solid electrochemical elemen~ of the present invention, there is used a foreign substance, namely, an insulating material which supports and surrounds a solid electrolyte. That is, the solid electrolyte material or the electrode material is surrounded by an insulating supporting material for solid electrolyte, preferably a plastic resin material, except for t.he portions which form an ion- or electron-conductive path optionally having a particular directionality. Accordingly, the insulating supporting substance for solid electrolyte is pushed into the gaps between the solid electrolyte particles or between the electrodP material particles in forming an ion - 6b -13094S~
1 conductor (a shaped material o~ solid electrolyte) or a shaped electrode material or in assembllng a solid electrochemical element, whereby an aggregate of particles is formed in which the neighbouring particles are in direct contact with one another and each particle i9 surrounded by the insulating supporting substance for solid electrolyte. As a result, the particles as a constituent member of the ion conductor, the electrode or the solid electrochemical element can keep a shape as an aggregate, can secure an electrical and ionic contact, and are not directly exposed to oxygen and moisture in the air and become unlikely to undergo deterioration.
These merits can be obtained more effectively by employing a step of crushing the solid electrolyte particles by pressing, in a process for producing an ion conductor (a shaped material of solid electrolyte), a shaped electrode material or a solid electrochemical element. When the solid electrolyte particles coated with a plastic resin (an insulating supporting substance for solid electrolyte) is crushed by pressing, there appear the surfaces thereof not coated with the plastic resin and, through these surfaces, there occur a direct contact between the solid electrolyte particles or between these particles and electrode particles. Thus, there can be obtained a sheet type ion conductor (a shaped material of solid electrolyte) with flexibility and excellent ion conductivity, as well as a shaped electrode material, and as a result there can be obtained a solid electrochemical 13094~6 1 element having an exc~llent mechanical strength and an excellent ~nvironmental resistance and capable of generating a large current.
The ion conductor of the present invention can also be formed in a sheet shape wherein surfaces of solid electrolyte particles are coated with an insulating supporting substance for solid electrolyte (e.g. a plastic resin) except for the particular surfaces, for example, the upper and lower surfaces. When two or more pairs of electrodes are provided on the upper and lower surfaces of the ion conductor, the electrodes cover and are contacted with the upper and lower portions of the solid electrolyte particles not coated with the insulating supporting substance, and thus the electrodes and the ion conductor are connected ionically. Within the ion conductor sheet, the ion does not move in the lateral direction but only in the vertical direction of the sheet, whereby no ionic flow occurs between the two neighbouring electrodes or between the two neighbouring but opposing electrodes. Thus, it is possible to constitute, using only one ion conductor sheet, a solid electrochemical element group consisting of a plurality of solid electrochemical elements which are electrically independent from one another, by providing two or more pairs of opposing electrodes on the two opposing surfaces of an ion conductor sheet.
In the present invention there is used an ion conductor consisting of solid electrolyte particles coated with an insulating supporting substance for solid ~3~g4~6 1 electrolyte, When this lon conductor is used in a solid electrochemical element, the upper and lower surfaces of the ion conductor are provided with electrodes. There-fore, the ion conductor may be produced in such a manner that the upper and lower surface on which electrodes are to be provided, may be coated very thinly or may not be coated substantially with an insulating supporting substance for solid electrolyte in order to obtain a good ionic contact between the ion conductor and the electrodes.
The insulating supporting substance for solid electrolyte according to the present invention can be any substance as long as it can surround solid electrolyte particles and can form a flexible aggregate of the solid electrolyte particles. Particularly, a plastic resin is preferred. As the plastic resin, there can be preferably used those which can be stably mixed with a solid electrolyte containing a high concentration of a chemi-cally active monovalent cation such as Na+, Li+, Ag+, Cu+, H+ or the like or with an electrode material as a strong oxidizing agent or a strong reducing agent. Such plastic resins are, for example, polyethylene, polypro-pylene, synthetic rubbers (e.g., styrene-butadlene rubber, Neoprene rubber), silicone resins, acrylic resins, etc.
When a polyethylene, polypropylene or acrylic resin is used, the fine powder of the resin is dry-blended with a solid electrolyte powder or grain or with an electrode material powder or grain. The particle diameter of the resin is preferably 1/10 to 1/10,000 time the _ g _ 1 particle diameter of each powder or grain. During the blendin~, the particles of the polyethylene, polypropylene or acrylic resin coat the surface of each particle of the powers or grains owing to the static electricity generated between the particles.
When a synthetic rubber such as styrene-butadiene rubber, Neoprene rubber or the like, a silicone resin or an acrylic resin is used, wet blending is conducted using an organic solvent such as toluene, xylene or the like.
That is, a synthetic rubber, an acrylic resin or a silicone resin is dissolved in an organic solvent in an amount of 5 to 20% by weight; to the solution is added a solid electrolyte powder or grain or an electrode material powder or grain; they are mixed and dispersed to obtain a ~a ~o~n~o~k~
fi~ slurry the slurry is casted on a Teflonlsheet; and the solvent is removed under vacuum, if necessary with heat-ing, whereby a shaped body can be obtained. Alterna-tively, the slurry itself can be treated under vaccum to remove the solvent and then shaped by pressing.
The solid electrolyte used in the present inven-tion includes Li+-conductive solid electrolytes such as LiI, LiI H2O, Li3N, Li4Sio4-Li3-Li3PO4, p Y
oxide-LiCF3SO3 and the like; Ag+-conductive solid electrolytes such as RbAg4I5, Ag3SI, AgI-Ag2O-MoO3 glass and the like; Cu+-conductive solid electrolytes such as RbCu I 5C13 5, RbCu4I1 25C13 75~ K0.2R 0.8 4 1.5 3.5 CuI-Cu2O-MoO3 glass and the like; H+-conductive solid 13094~6 1 electrolyteS such as H3Mol2P40 29H2~ 3 12 40 2 the like; and Na+-conductive solid electrolytes represent-ed by Na-~-A1203 (sodium ~-alumina) or Nal+xZr2P3 xSix012 ~0 ~ x ~ 3).
As the electrode material of the present inven-tion, there can be used, for example, carbon materials such as graphite, acetylene black, active carbon and the like: sulfides such as titanium sulfide, niobium sulfide, cuprous sulfide, silver sulfide, lead sulfide, iron sulfide and the like; oxides such as tungsten oxide, vanadium oxide, chromium oxide, molybdenum oxide, titanium oxide, iron oxide, silver oxide, copper oxide and the like; halides such as silver chloride, lead iodide, cuprous iodide and the like; and metal materials such as copper, silver, lithium, gold, platinum, titanium and their alloys.
A solid electrolyte cell or battery can be constituted by combining an ion conductor (a shaped material of solid electrolyte particlesl and an electrode material which can give ion to the ion conductor or receive ion therefrom, such as titanium disulfide or the like.
A solid electrochemical display element (a solid electrochromic display) can be constituted by using an ion conductor and an electrode material which can give or receive ion and simultaneosuly causes an optical change, such as tungsten oxide or the like.
A solid electrical double layer capacitor can be ~3094~6 1 constituted by using an ton conductor and an electrode material which does not glve or receive ion but can form an electrical double layer at the interface with the ion conductor, such as active carbon or the like.
All of these solid electrochemical elements according to the present invention have a sufficient flxibility, an excellent mechanical strength and an excellent environmental resistance.
A solid electrolyte, for example, a powder of RbCu4I1 5C13 5 of 200 mesh pass through 100% is dispersed in a toluene solution of a styrene-butadiene copolymer so that the volume fraction of the powder after drying becomes 85~. The resulting slurry is spread on a Teflon sheet using an applicator bar and they are placed in dry air to remove toluene, whereby a flexible sheet type ion conductor (a shaped material of solid electrolyte particles) having no fluidity is obtained. This ion conductor can be used as it is for constitution of a solid electrochemical element but, by rolling it with a roller press so as to have a thickness of about 2/3 or less of the original thickness, can be made into a sheet type ion conductor with improved ion conductivity wherein the solid electrolyte particles have been crushed by pressing.
A shaped electrode material can also be formed in a similar manner. In forming a shaped electrode material using, for example, copper as an electrode material, a copper powder having particle diameters of 5 microns or less and a RbCu4I1 5C13 5 powder having 13094~6 1 particle diameters of 200 me~h pass through 100% are mixed at a weight ratio of 90 : 10. The mixed powder is dispersed in a toluene solution of a styrene-butadiene copolymer so that the volume fraction of the mixed powder after drying becomes 90~. The resulting slurry is spread on a Teflon sheet using an applicator bar and they are placed in dry air to remove toluene, whereby a flexible sheet type shaped electrode ma~erial is obtained. It can be rolled by a roller press to have a thickness of about 2/3 or less of the original thickness, whereby an elec-trode having an excellent electrical conductivity and an excellent ionic conductivity can be obtained.
By press-molding the ion conductor interposed between the shaped electrode materials thus obtained together with, if necessary, other constituent members such as a current collector into one integral body, a solid electrochemical element can be obtained.
Production of a solid electrochemical element - can be conducted as above by making a shaped ion conductor and a shaped electrode material into one integral body.
Alternatively, it can be conducted by directly shaping the respective powders or grains coated with a plastic resin into one integral body.
The present invention will be described in detail below by way of Examples and Comparative Examples.
Example 1 Fig. 1 shows the structure of an ion conductor 13094~6 1 according to the present invention. Fig. l~a) is a plane view of the ion conductor and Fig. l(b) i~ a sectional view obtained by cutting the ion conductor of Fig. l(a) at a line C. In Figs. l(a) and l(b), 1 is a particulate solid electrolyte and 2 is an insulating supporting substance ~or solid electrolyte. The slant line portions are the portions of the particulate solid electrolyte hidden by the insulating supporting substance for solid electrolyte. RbCu4I1 5C13 5 as a particulate solid elec-trolyte was ground with a ball mill under dry air, andonly the solid electrolyte having particle diameters of 80 to 100 microns was used by sieving. A silicone rubber was used as a supporting substance for solid electrolyte.
Preparation of an ion conductor was conducted according to Fig. 2. Firstly, the above two materials were mixed at a ratio of 1 : 1 by weight. Mixing was conducted thoroughly using toluene as a solvent in order to sufficiently disperse the particulate solid electrolyte in the silicone rubber. The resulting mixture 4 was screen-printed on a stainless steel substrate 3 with a spatula 6 using a stainless steel screen 5 of 100 mesh through [see Fig.
2(a)]. Then, toluene was vaporized [see Fig. 2(b)].
Subsequently, the particulate solid electrolyte supported by the silicone rubber was rolled together with a silicone rubber 9 between two rollers 7 and 8 whose gaps had been adjusted to 100 microns to obtain an ion conductor sheet having a thickness of 100 microns [see Fig. 2(c)]. This ion conductor sheet showed an anisotropy with respect to 1~094~6 1 the ion conductivity. The ion conductivity at 25C was 4.5 x 10 2 n lcm 1 in the thickness direction and 7.3 x 10 12 Q lcm 1 in the lateral direction.
Examples 2 to 4 S Vsing other particulate solid electrolytes and supporting substances for solid electrolyte, ion con-ductors were prepared in the same manner as in Example 1.
Each ion conductor showed an anisotropy with respect to the ion conductivity. The results are shown in Table 1.
C l l l o o o o ~-V , , , ~ t, X X X
.~ ~J ~ D
.~ ~ ~ ~ ~ ~
Ul _ C~O ~C l l l o I ~g o o o o C~ C~ V ,, , ,, o o ~ X X
H S -~ 1~'1 t~l OD
E-l~ ~D ~` I_ C C C
~ ~> ~ ~
O O ~ O
ca E l 1:~ E~
a c a~ ~ ~ a~
aJ ~ I C Q) Q
~1 v c ,i O a Q Ll ~a O ~ C-,l sl a) ~ O ~_I
11~ o v u~ v a~ ~ a) Ll Q~ I~ ~
E-~ ~ IQ t> ~ a Q S2~ Q r~ Q
~Q Ll ~ :~1V 5:~ O .a ~I Q
:~ :J o _I v :~ ~ a) ~ .,~ :~
u~ 1 a) u~ Q ~-I Z ~-I tQ
~_ ~
C 0,~
V Ll ~ O
~ O .,1 ~O ~ ~
O .~ ~3 C 5 Ll V O O V O ~>
v ~ 0~ e o~ ~
a ~ P. o ~ o ~ ~ o o O
~ ~ r~ _i æ _i r~ ~ ~ ~ ~ _ o ~: o ~ ~ ~ er X
13094~6 1 Example 5 NASICON ~Na-super ion conductor), a Na -conduc-tive solid electrolyte represented by Nal+xZr2P3_xSixOl2 (0 ~ x ~ 3) was ground so as to have particle diameters of 100 ~ 10 microns, and these particles were used as a particulate solid electrolyte. A polyethylene powder having a particle diameter of 100 microns was used as a supporting substance for solid electrolyte. In order to prepare an ion conductor sheet, the particulate solid electrolyte and the polyethylene powder were mixed; the mixture was melted at 200C; and the melt was rolled between hot rollers whose gaps had been adjusted to 100 microns to obtain a sheet. The temperature of the hot rollers was set at 30C. The sheet had ion conductivities of 7.3 x 10 5 Q lcm 1 in the thickness direction and 2.6 x 10 13 Q lcm 1 in the lateral direction. By melting, the polyethylene could effectively surround each solid elec-trolyte particle.
Example 6 An ion conductor sheet was prepared in the same manner as in Example 5 except that the polyethylene as a supporting substance for solid electrolyte was changed to a polypropylene resin. The sheet had ion conductivities of 5.4 x 10 5 Q lcm 1 in the thickness direction and ~.1 x 10 13 Q lcm 1 in the lateral direction.
-13~94~6 1 Example 7 Another embodlment of the ion conductor accord-ing to the present invention is shown in Fig. 3. A sheet 10 of a polyethylene oxide (PE0)-LiCF3S03 polymer elec-trolyte having a thickness of 100 microns was used as asolid electrolyte. The sheet was prepared by mlxing LiCF3S03 and a PE0 having a molecular weight of 750,000, dissolving the mixture in acetonitrile, casting the solution on a stainless steel plate, and vaporizing the solvent at 70C. Separately, a sheet 11 of the PE0 alone was prepared in a similar manner. The two sheets were stacked alternately ~see Fig. 3(a)], and the laminate was cut at a line B to prepare a zebra-patterned sheet [see Fig. 3(b)]. The sheet was measured for ion conduc-tivities regarding the surfaces a, b and c. They were 3.4x 10 6 Q lcm 1 between the surfaces a and b and 7.1 x 10 13 Q lcm 1 between the surfaces b and c.
Example 8 An ion conductor sheet was prepared in the same manner as in Example 1 except that 60~ by weight of white insulating particles of TiO2 (70 microns in particle diameter) had been added to the silicone rubber of Example 1. The sheet had ion conductivities of 5.7 x 10 3 Q lcm 1 in the thickness direction and 2.2 x 10 13 Q lcm 1 in the lateral direction A laminate type thin film battery was prepared using an ion conductor prepared as above. The preparation ~o~
1 process is shown in Fig. 4. The positive electrode group of the battery is shown in Fig, 4~a) and the negative electrode group is shown in Fig. 4(b). The positive electrode group was prepared by vapor-depositing stainless steel on a glass substrate through a mask to form stain-less steel portions 13, 15 and 17 and then vapor-deposit-ing thereon CuI through a mask to form CuI portions 14 in a thickness of 3,000 ~ [see Fig. 4(a)]. The portions 15 and 17 later become a positive electrode terminal and a negative electrode terminal, respectively. In a similar manner, the negative electrode group was prepared by vapor-depositing stainless steel on a glass substrate 12 through a mask to form stainless steel portions 13 and then vapor-depositing thereon copper through a mask to ~orm copper portions 16 [see Fig. 4(b)]. The above mentioned ion conductor sheet consisting of a particulate solid electrolyte 1 and a supporting substance 2 for solid electrolyte was put between the positive electrode group and the negative electrode group so that the electrode groups faced each other, and the circumference of the resulting laminate was coated with an epoxy adhesive 18, whereby a battery was prepared [see Fig. 4(d)]. The connection of the electrode groups was conducted using indium metal 19. The resulting battery was measured for electromotive force, and a voltage of 1.8 V existed between the positive electrode terminal 15 and the negative electrode terminal 17. Since the electromotive force of this battery was 0.6 V per single cell, it was ~309~6 1 found that the use of an ion conductor sheet according to this invention makes it unnecessary to divlde the electrolyte into each single cell portion. Further, in order to examine an effect when a plastic supporting substance for solid electrolyte is used, a battery was constituted by using, as a substrate 12 for each electrode group, a polyimide film having a thickness of 0.4 mm. As a result, it was found that the battery had an excellent elasticity. Therefore, this battery was found to be suitable for use as an electric source for IC cards requiring an elasticity. It was further found that the ion conductor sheet containing insulating particles, prepared in Example 8, when put between transparent electrodes, produced a sharp pink color on a white back-ground due to the precipitation of copper when a voltage was applied between the transparent electrodes and accordingly is suitable for use as an electrolyte for electrochromic display.
Example 9 A powder of 5 microns or less as particulate solid electrolyte was sufficiently mixed with a toluene solution containing 10~ of a styrene-butadiene copolymer, in a volume ratio of 85 (solid electrolyte) to 15 (copolymer~. In mixing, a suitable amount of toluene was used as a diluent.
The mixture thus prepared was a slurry having slight fluidity. The slurry was extended on a Teflon 1309~6 1 sheet in a thickness of 100 microns using an applicator bar. Toluene was vap~rized ln dry air and then the dried ~ilm was rolled into a film thickness of 70 microns using a roller press to crush the solid electrolyte particles, whereby a desired ion conductor was obtained.
In order to measure the ion conductivity, the ion conductor was cut into specimen of 1 cm2. On the two surfaces of the specimen were provided two copper electrodes each having the same size as the specimen, in a sandwich form. This was done by wetting the ion conductor surfaces with toluene and then pressing the electrodes thereon. Subsequently, an AC having a voltage of 10 mV
and a frequency of 1 KHz was applied between the two electrodes and the resulting AC resistance was measured.
It was 1.5 x 10 4 S/cm2.
In a comparative test for examining the effect of crushing by pressing, an ion conductor sheet was prepared according to the following manner. As a particulate solid electrolyte, there was used a powder having particle diameters of 1 micron or less which was difficult to be crushed by rolling, and an ion conductor sheet was prepared in the same manner as in Example 9.
The resulting ion conductor showed a low ion conductivity of 9.5 x 10-6 S/cm2.
An ion conductor sheet was prepared in the same manner as in the sheet of Example 9 except that crushing and rolling was conducted using an ordinary press in place of the roller press. That is, the ion conductor sheet 1309~
1 before crushing and rolling was sandwiched be~ween two stainless steel plates (in the form of a square of 10 cm x 10 cm having a thickness of 1 cm); using spacers of 70 microns in thickness, a pressure of 1 ton/cm2 was applied by a press to crush the solid electrolyte particles. The resulting ion conductor sheet had an ion conductivity of 9.7 x 10-5 S/cm2.
The reason is not clear yet but roller pressing, as compared with ordinary pressing by a press, can crush solid electrolyte particles more effectively and can provided an ion conductor with superior ion conductivity.
Example 10 100 parts by weight of a solid electrolyte, namely, a powder of a Cu+-conductive solid electrolyte represented by RbCu4I1 5C13 5, having an average particle diameter of 10 microns was mixed with 20 parts by weight of a polyethylene powder having an average particle diameter of 0.1 micron in a dry nitrogen atmosphere. The mixture was formed into a shaped solid electrolyte material of 5 mm x 20 mm x 100 microns (thickness) using a roller press at a pressure of 200 kg/cm2. In a similar manner, there was obtained a shaped positive electrode material of 5 mm x 20 mm x 200 microns (thickness) consisting of 50 parts by weight of a powder of a positive electrode active substance represented by CuO lNbS2, having an average particle diameter of 15 microns, 50 parts by weight of the above mentioned solid electrolyte -" 1309456 1 powder and lS parts by weight of the above mentioned polyethylene powder. Also in a similar manner, there was obtained a shaped negative electrode material of 5 mm x 20 mm x 120 microns (thickness) consisting of 50 parts by weight of a powder of a negative electrode active substance tmetallic copper) having an average particle diameter of 8 microns, 50 parts by weight of the above mentioned solid electrolyte powder and 25 parts by weight of the above mentioned polyethylene powder. These shaped materials were stacked in three layers and a pressure of 250 kg/cm2 was applied thereto, whereby a copper type solid cell A was obtained as an integral body.
Example 11 A copper type solid cell B was obtained in the same manner as in Example 10 except that a polypropylene powder having an average particle diameter of 0.1 micron was used in place of the polyethylene powder.
Comparative Example 1 A copper type solid cell C was obtained in the same manner as in Example 10 except that no polyethylene powder was used.
Example 12 An Ag type solid cell D was obtained in the same manner as in Example 10 except that there were used, as a solid electrolyte, a powder of an Ag+-conductive solid 13094~6 1 electrolyte represented by ~bAg4I5, having an average particle diameter of 8 microns, as a positive electrode active substance, a powder of AgO lNbS2 having an average particle diameter of 15 microns, and as a negative elec-trode active substance, a powder of metallic silver havingan average particle diameter of 8 microns.
Comparative Example 2 An Ag type solid cell E was obtained in the same manner as in Example 12 except that no polyethylene powder was used.
Example 13 A Li type solid cell F was obtained in the same manner as in Example 10 except that there were used, as a solid electrolyte, a powder of a Li+-conductive solid electrolyte represented by LiI, having an average particle diameter of 15 microns, as a positive electrode active substance, a powder of WO3 having an average particle diameter of 12 microns, and as a negative electrode active substance, a powder of Lil 5WO3 having an average particle diameter of 10 microns.
Comparative Example 3 A Li type solid cell G was obtained in the same manner as in Example 13 except that no polyethylene powder was used.
1 Example 14 An H type solid cell H was obtained in the same manner as in Example 10 except that there were used, as a solid electrolyte, a powder of a H+-conductive solid S electrolyte represented by H3Mol2PO40 29H2O, having an average particle diameter of 20 microns, as a positive electrode active substance, a powder of WO3 having an average particle diameter of 8 microns, and as a negative electrode active substance, a powder of HWO3 having an average particle diameter of 8 microns, and the polyethy-lene powder was changed to an acrylic resin powder having an average particle diameter of 0.2 micron.
Comparative Example 4 An H type solid cell I was obtained in the same manner as in Example 14 except that no acrylic resin powder was used.
Example 15 100 parts by weight of a solid electrolyte, namely, a powder of a Cu+-conductive solid electrolyte represented by RbCu4I1 25C13 75, having an average particle diameter of 2 microns was mixed with 30 parts by weight of a toluene solution containing 10% by weight of a styrene-butadiene rubber to obtain a solid electrolyte slurry. The slurry was extended on a fluoresin plate using a bar coater in a thickness (when dried~ of 20 microns and then dried for 3 hours at 50C under a reduced 1309~56 1 pressure of 1 Torr, whereby a solid electrolyte thin film of 60 mm (width) x 800 mm ~length) x 20 microns (thick-ness) was obtained.
Separately, 50 parts by weight of a graphite powder having an average particle diameter of 0.5 micron and 50 parts by weight of the above mentioned solid electrolyte powder were mixed with 35 parts by weight of the above mentioned toluene solution to obtain a positive electrode slurry. In a similar manner and using this slurry, there was obtained a positive electrode thin film of 60 mm (width) x 800 mm (length) x 30 microns (thick-ness).
Separately, 50 parts by weight of a metallic copper powder having an average particle diameter of 2 microns, 50 parts by weight of the above mentioned solid electrolyte powder and 18 parts by weight of the above mentioned toluene solution were mixed to obtain a negative electrode slurry. In a similar manner and using this slurry, there was obtained a negative electrode thin film of 60 mm (width) x 800 mm (length) x 20 microns (thick-ness).
Then, the positive electrode thin film was provided on one surface of the solid electrolyte thin film and the negative electrode thin film was provided on the other surface of the solid electrolyte thin film. They were shaped into one integral body at a pressure of 20 kg/cm using a roller press of 130 to 150C to obtain a thin film of 65 mm (width) x 1,000 mm (length) x 55 to 65 13094~6 1 microns ~thickness). This thin film was cut into pieces of 5 mm x 20 mm to obtain a solid cell J.
Example 16 A solid cell K was obtained in the same manner as in Example 15 except that the styrene-butadiene rubber was changed to a silicone resin.
Example 17 A solid cell L was obtained in the same manner as in Example 15 except that the styrene-butadiene rubber was changed to an acrylic resin.
Example 18 on the two surfaces of a solid electrolyte film having a thickness of 20 microns, obtained in the same manner as in Example 15, were provided an electrode film having a thickness o~ 30 microns and consisting of a graphite powder, a solid electrolyte powder and a styrene-butadiene rubber, obtained in the same manner as in Example 15. They were shaped into one integral body at a pressure of 20 kg/cm2 and at 130 to 150C using a roller press to obtain a sheet of 65 mm (width) x 1,000 mm (length) x 60 to 65 microns (thickness). The sheet was cut into pieces of 5 mm x 20 mm to obtain a solid electri-cal double layer capacitor M.
13094~6 1 Example 19 50 parts by weight o~ a solid electrolyte, namely, a powder of a H+-conductive solid electrolyte y 3Mol2PO40 29H2O, having an average particle diameter of 20 microns, 20 parts by weight of an acrylic resin powder having an average particle diameter of 0.2 micron and a graphite powder having an average particle diameter of 0.5 micron were mixed and shaped in the same manner as in Example 10 to prepare a graphite 10 electrode of 5 mm x 20 mm x 30 microns (thickness). Three layers comprising in the following order (a) the above electrode, (b) a solid electrolyte film of 5 mm x 20 mm x 50 microns (thickness) consisting of a H+-conductive solid electrolyte and an acrylic resin and (c) a display 15 electrode of 5 mm x 20 mm x 10 microns (thickness) containing tungsten trioxide (WO3), prepared in the same manner as in Example 14 were pressed into one body, whereby a solid electrochromic display element N of 5 mm x 20 mm x 85 microns (thickness) was assembled.
The above prepared solid cells A to L, solid electrical double layer capacitor M and solid electro-chromic display element N were subjected to repeated bending test (30 bending in the longitudinal direction).
The number of times of bending until breakage occured in each test is shown in Table 2. Also shown in Table 2 is the ratio of RltRo of each of the elements A to N wherein : Rl is the internal resistance of an element when the element has been allowed to stand for 48 hours in an 13094~6 1 atmosphere of 45C and 60~ humldity and Ro is the initial internal resistance of the element.
All of the solid electrochemical elements A, B, D, F, H, J, K, L, M and N according to the present inven-tion can withstand bending of several hundred times to several thousand times, and any of them does not show a noticeable increase in the internal resistance, when allowed to stand in the atmosphere. Meanwhile, the solid electrochemical elements C, E, G and I for comparison have no flexibility at all and are broken in bending of only one time and, when allowed to stand in the atmosphere, show a significant increase in the internal resistance.
~"` ~3094~i6 n -- 3~ --
Claims (17)
1. A solid electrochemical element which is flexible, has improved mechanical strength, and has improved stability upon exposure to the environment, comprising:
at least one solid electrolyte sheet which is flexible, has a pair of opposing surfaces, and is comprised of solid electrolyte particles and a plastic resin, which plastic resin was coated on each particle of said solid electrolyte particles prior to formation of said at least one solid electrolyte sheet; and at least two electrode sheets comprised of an electrode material, one of said at least two electrode sheets being joined to each of said pair of opposing surfaces of said at least one solid electrolyte sheet, wherein the at least one solid electrolyte sheet has a thickness and the solid electrolyte particles have a particle diameter which does not exceed the thickness of the at least one solid electrolyte sheet.
at least one solid electrolyte sheet which is flexible, has a pair of opposing surfaces, and is comprised of solid electrolyte particles and a plastic resin, which plastic resin was coated on each particle of said solid electrolyte particles prior to formation of said at least one solid electrolyte sheet; and at least two electrode sheets comprised of an electrode material, one of said at least two electrode sheets being joined to each of said pair of opposing surfaces of said at least one solid electrolyte sheet, wherein the at least one solid electrolyte sheet has a thickness and the solid electrolyte particles have a particle diameter which does not exceed the thickness of the at least one solid electrolyte sheet.
2. The solid electrochemical element according to claim 1, wherein each of the at least two electrode sheets is comprised of electrode material in particulate form and wherein each of the at least two electrode sheets is comprised of a mixture of electrode material particles and solid electrolyte particles.
3. The solid electrochemical element according to claim 2, wherein at least one of the electrode material particles and the solid electrolyte particles of the at least two electrode sheets is coated with a plastic resin.
4. The solid electrochemical element according to claim 1, wherein the solid electrolyte particles are monovalent cation-conductive solid electrolyte particles.
5. The solid electrochemical element according to claim 1, wherein the plastic resin is at least one plastic resin selected from the group consisting of polyethylene, polypropylene, styrene-butadiene rubber, Neoprene rubber, silicone rubber, silicone resin, and acrylic resin.
6. A process for producing a solid electrochemical element which is flexible, has improved mechanical strength and has improved stability upon exposure to the environment, the process comprising:
a. separately dispersing electrode material particles and solid electrolyte particles in solvent containing a plastic resin dissolved therein to provide respective dispersions; b. evaporating solvent from each respective dispersion of step a to form powdery particles, their aggregates or their moldings, consisting of particles coated with plastic resin; c. forming at least one solid electrolyte sheet and at least two electrode sheets from the powdery particles, their aggregates or their moldings, respectively comprised of solid electrolyte particles coated with plastic resin and electrode material particles coated with plastic resin, wherein said at least one solid electrolyte sheet is flexible, has a pair of opposing surfaces, and has a thickness, wherein the solid electrolyte particles have a particle diameter which does not exceed the thickness of the at least one solid electrolyte sheet, and wherein said at least two electrode sheets are flexible: and d. joining one of the at least two electrode sheets to each pair of opposing surfaces of the at least one solid electrolyte sheet to form the solid electrochemical element.
a. separately dispersing electrode material particles and solid electrolyte particles in solvent containing a plastic resin dissolved therein to provide respective dispersions; b. evaporating solvent from each respective dispersion of step a to form powdery particles, their aggregates or their moldings, consisting of particles coated with plastic resin; c. forming at least one solid electrolyte sheet and at least two electrode sheets from the powdery particles, their aggregates or their moldings, respectively comprised of solid electrolyte particles coated with plastic resin and electrode material particles coated with plastic resin, wherein said at least one solid electrolyte sheet is flexible, has a pair of opposing surfaces, and has a thickness, wherein the solid electrolyte particles have a particle diameter which does not exceed the thickness of the at least one solid electrolyte sheet, and wherein said at least two electrode sheets are flexible: and d. joining one of the at least two electrode sheets to each pair of opposing surfaces of the at least one solid electrolyte sheet to form the solid electrochemical element.
7. The process for producing a solid electrochemical element according to claim 6, wherein, in step d, joining is accomplished by pressing in which at least one of the electrode material particles and the solid electrolyte particles is crushed by the pressing.
8. The process for producing a solid electrochemical element according to claim 6, wherein the solid electrolyte particles are monovalent cation-conductive solid electrolyte particles.
9. The process for producing a solid electrochemical element according to claim 6, wherein the plastic resin is at least one plastic resin selected from the group consisting of polyethylene, polypropylene, styrene-butadiene rubber, Neoprene rubber, silicone rubber, silicone resin, and acrylic resin.
10. The process for producing a solid electrochemical element according to claim 7, wherein pressing is accomplished in a roller press and wherein the solid electrolyte particles are crushed by the roller press.
11. The process for producing a solid electrochemical element according to claim 6, wherein each of the at least two electrode sheets further comprises solid electrolyte particles which were dispersed in step a with the electrode material particles in solvent containing a plastic resin dissolved therein.
12. The process for producing a solid electrochemical element which is flexible, has improved mechanical strength and has improved stability upon exposure to the environment, the process comprising:
a. separately mixing solid electrolyte particles and electrode material particles with plastic resin powder to provide respective mixtures; b. separately forming using heat at least one solid electrolyte sheet and at least two electrode sheets from the respective mixtures of step a respectively comprised of solid electrolyte particles and plastic resin powder, and electrode material particles and plastic resin powder, wherein said at least one electrolyte sheet is flexible, has a pair of opposing surfaces, and has a thickness, wherein the solid electrolyte particles have a particle diameter which does not exceed the thickness of the at least one solid electrolyte sheet, and wherein said at least two electrode sheets are flexible, and c. joining one of the at least two electrode sheets to each of the pair of opposing surfaces of the at least one solid electrolyte sheet to from the solid electrochemical element.
a. separately mixing solid electrolyte particles and electrode material particles with plastic resin powder to provide respective mixtures; b. separately forming using heat at least one solid electrolyte sheet and at least two electrode sheets from the respective mixtures of step a respectively comprised of solid electrolyte particles and plastic resin powder, and electrode material particles and plastic resin powder, wherein said at least one electrolyte sheet is flexible, has a pair of opposing surfaces, and has a thickness, wherein the solid electrolyte particles have a particle diameter which does not exceed the thickness of the at least one solid electrolyte sheet, and wherein said at least two electrode sheets are flexible, and c. joining one of the at least two electrode sheets to each of the pair of opposing surfaces of the at least one solid electrolyte sheet to from the solid electrochemical element.
13. The process for producing a solid electrochemical element according to claim 12, wherein the solid electrolyte particles are monovalent cation-conductive solid electrolyte particles.
14. The process for producing a solid electrochemical element according to claim 12, wherein the plastic resin is at least one plastic resin selected from the group consisting of polyethylene, polypropylene, and acrylic resin.
15. The process for producing a solid electrochemical element according to claim 12, wherein, in step c, joining is accomplished by pressing in which at least one of the solid electrolyte particles and the electrode material particles is crushed by the pressing.
16. The process for producing a solid electrochemical element according to claim 15, wherein pressing is accomplished in a roller press and wherein the solid electrolyte particles are crushed by the roller press.
17. The process for producing a solid electrochemical element according to claim 12, wherein each of the at least two electrode sheets further comprises solid electrolyte particles which were mixed in step a with the electrode material particles.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP223101/86 | 1986-09-19 | ||
JP61223101A JPS6378405A (en) | 1986-09-19 | 1986-09-19 | Anisotropic ion conductor |
JP26340886 | 1986-11-05 | ||
JP263408/86 | 1986-11-05 | ||
JP62072405A JP2666276B2 (en) | 1987-03-26 | 1987-03-26 | Method for producing electrochemical element member containing solid electrolyte |
JP72405/87 | 1987-03-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1309456C true CA1309456C (en) | 1992-10-27 |
Family
ID=27300941
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 546422 Expired - Lifetime CA1309456C (en) | 1986-09-19 | 1987-09-09 | Solid electrochemical element and production process thereof |
Country Status (6)
Country | Link |
---|---|
US (1) | US4977007A (en) |
EP (1) | EP0260679B1 (en) |
KR (1) | KR900007731B1 (en) |
CN (1) | CN1022273C (en) |
CA (1) | CA1309456C (en) |
DE (1) | DE3785901T2 (en) |
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-
1987
- 1987-09-08 US US07/097,367 patent/US4977007A/en not_active Expired - Lifetime
- 1987-09-09 CA CA 546422 patent/CA1309456C/en not_active Expired - Lifetime
- 1987-09-16 EP EP19870113550 patent/EP0260679B1/en not_active Expired - Lifetime
- 1987-09-16 DE DE19873785901 patent/DE3785901T2/en not_active Expired - Fee Related
- 1987-09-18 CN CN87107102A patent/CN1022273C/en not_active Expired - Fee Related
- 1987-09-18 KR KR1019870010356A patent/KR900007731B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
KR880004595A (en) | 1988-06-07 |
US4977007A (en) | 1990-12-11 |
KR900007731B1 (en) | 1990-10-19 |
DE3785901D1 (en) | 1993-06-24 |
DE3785901T2 (en) | 1993-12-16 |
CN87107102A (en) | 1988-06-15 |
EP0260679B1 (en) | 1993-05-19 |
CN1022273C (en) | 1993-09-29 |
EP0260679A3 (en) | 1991-01-02 |
EP0260679A2 (en) | 1988-03-23 |
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