US20010012193A1 - Non-aqueous electrolyte cells and electric double layer capacitors - Google Patents

Non-aqueous electrolyte cells and electric double layer capacitors Download PDF

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US20010012193A1
US20010012193A1 US09767506 US76750601A US2001012193A1 US 20010012193 A1 US20010012193 A1 US 20010012193A1 US 09767506 US09767506 US 09767506 US 76750601 A US76750601 A US 76750601A US 2001012193 A1 US2001012193 A1 US 2001012193A1
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concave
shaped container
container
bottom surface
collector
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US6445566B2 (en )
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Shunji Watanabe
Tsugio Sakai
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Shunji Watanabe
Tsugio Sakai
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/155Double-layer capacitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/04Hybrid capacitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/02Cases, jackets or wrappings
    • H01M2/0257Cases, jackets or wrappings characterised by the material
    • H01M2/0262Cases, jackets or wrappings characterised by the material for large-sized cells or batteries, batteries or cells for traction or motive power or standby power
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/02Cases, jackets or wrappings
    • H01M2/0257Cases, jackets or wrappings characterised by the material
    • H01M2/027Casing material forming terminal of the cell
    • H01M2/0272Casing material forming terminal of the cell characterized by the internal coating or internal conductive layer
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/02Cases, jackets or wrappings
    • H01M2/0257Cases, jackets or wrappings characterised by the material
    • H01M2/0275Cases, jackets or wrappings characterised by the material of flexible envelopes or bags around open cell elements
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/02Cases, jackets or wrappings
    • H01M2/0257Cases, jackets or wrappings characterised by the material
    • H01M2/0277Insulating material
    • H01M2/028Insulating material being one layer
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/02Cases, jackets or wrappings
    • H01M2/0257Cases, jackets or wrappings characterised by the material
    • H01M2/0287Cases, jackets or wrappings characterised by the material comprising layers
    • H01M2/029Cases, jackets or wrappings characterised by the material comprising layers consisting only of insulating material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/13Ultracapacitors, supercapacitors, double-layer capacitors

Abstract

An electric double layer capacitor affords cost reduction and miniaturization. In a non-aqueous electrolyte cell and an electric double layer capacitor, which are composed of active materials used as a cathode and an anode, and a container for receiving the materials and an electrolyte, the storage container is composed of a concave-shaped container 101 and a sealing plate 102, and first and second collectors disposed in the container are electrically connected to joining terminals A103, B104 disposed on an outer bottom surface and/or sides of the container, the joining terminals A103, B104 being made integral with the storage container.

Description

    BACKGROUND OF THE INVENTION
  • The invention relates to a non-aqueous electrolyte cell capable of being mounted on a surface and an electric double layer capacitor making use of electric double layer theory. [0001]
  • Non-aqueous electrolyte cells and electric double layer capacitors have been conventionally used as backup power sources for clock function, backup power sources for memories of semiconductors, standby power sources for electronic devices such as microcomputers, IC memories and the like, cells for solar watches, and electric power sources for driving of motors, and have been investigated as electric power sources for electric automobiles and auxiliary power storage units of energy transformation and storage systems in recent years. [0002]
  • For backup power sources, high capacity and electric current for driving of semiconductors have been hitherto needed. In recent years, however, semiconductor memories have been put into use, which have no need of backup power sources owing to improvements in the technology of nonvolatile memory. Also, low power consumption has been promoted in elements with clock function. Accordingly, there has been reduced the need for non-aqueous electrolyte cells and electric double layer capacitors, which require substantially large capacity and electric current. [0003]
  • A non-aqueous electrolyte cell or an electric double layer capacitor is constructed as shown in FIG. 2. A positive active material [0004] 201 is bonded to a positive electrode case 202 with an electrode collector 202 and negative active material 204 is bonded to a negative electrode case 205 with another electrode collector 202. The negative electrode case 205 is inserted into the groove for the gasket 207. With the electorolyte 206 added, the negative electrode case 205 and positive electrode case 203 are combined together and the case 203 is crimped for sealing.
  • The need for non-aqueous electrolyte cells and electric double layer capacitors, which require substantially large capacity and electric current, has been reduced due to the fact that nonvolatile memories have prevailed and low power consumption has been promoted in elements with clock function. Rather, with respect to non-aqueous electrolyte cells and electric double layer capacitors, the demand has been increased for thinning of them and reflow soldering (a method of soldering, comprising beforehand applying a soldering cream or the like on those portions on a printed circuit board, which are to be subjected to soldering to place parts on the portions, or after such placing of parts, supplying small soldering balls (soldering bumps) to portions being subjected to soldering, and passing the printed circuit board with parts thereon through a furnace under high temperature atmosphere set so that portions being subjected to soldering become above the melting point of solder, for example, 200 to 230° C., to thereby melt solder). [0005]
  • Since conventional non-aqueous electrolyte cells and electric double layer capacitors have a cross section shown in FIG. 2 to be circular like coins and buttons, reflow soldering entails the need of beforehand welding terminals or the like to a casing, with the result that the cost goes up in terms of an increase in the number of parts and in manufacturing manhour. Also, it is necessary to provide on the board a space for terminals, and so limitation is imposed on making the cells and capacitors small in size. [0006]
  • SUMMARY OF THE INVENTION
  • In a non-aqueous electrolyte cell and an electric double layer capacitor, which are composed of active materials used as a cathode and an anode, and a container for receiving the materials and an electrolyte, the container is composed of a concave-shaped container and a sealing plate. [0007]
  • The concave-shaped container of the receiving container is made of a good heat-resistant material such as heat resisting resins, glass, ceramics or ceramic glass, and a metallic layer is formed on the inner bottom surface of the concave-shaped container to make a first collector to be electrically connected to a joining terminal A disposed on the outer bottom surface of the concave-shaped container. [0008]
  • Also, a metallic layer is formed on an edge of the concave-shaped container to be electrically connected to a joining terminal B disposed on the outer bottom surface of the concave-shaped container. A cathode active-material, a separator, and an anode active-material, which are made to be sheet-shaped, are stackingly inserted in the concave-shaped container. [0009]
  • Joining terminals A, B are formed on either the outer bottom surface and sides of the concave-shaped container or either of the outer bottom surface and sides in such a manner to eliminate short-circuiting. [0010]
  • Subsequently, a bonding material, such as a brazing material or a solder material, having a configuration substantially identical to that of the edge of the concave-shaped container is placed on the edge of the concave-shaped container to be interposed between it and the sealing plate. The sealing plate may be formed of a metal or a good heat-resistant material such as a heat-resistant resin with a metallic layer, glass, ceramics or ceramic glass or the like. [0011]
  • The sealing plate is heated to above the melting point of the bonding material, such as a brazing material or a solder material, and pressurized for sealing. [0012]
  • Since the joining terminals are made integral with the receiving container and disposed on a lower portion of the receiving container, it becomes possible to decrease space in the form of a sheet. [0013]
  • Thus, the invention provides a non-aqueous electrolyte cell and an electric double layer capacitor, which are composed of active materials used as a cathode and an anode, and a container for receiving the materials and an electrolyte, and in which the container is composed of a concave-shaped container and a sealing plate, and the concave-shaped container is provided on an inner bottom surface thereof with a first collector, which is electrically connected to a joining terminal A disposed on an outer bottom surface and/or sides of the concave-shaped container, the sealing plate being provided on a surface inside the cell with a second collector, which is electrically connected to a joining terminal B disposed on an outer bottom surface and/or sides of the concave-shaped container. In this case, the sealing plate on the second collector is electrically connected to a joining terminal B through the metallic layer on the edge of the concave-shaped container and bonding material. [0014]
  • Also, the first collector and the joining terminals disposed on the concave-shaped container of the receiving container and the metallic layer on the edge of the container are composed of a material having a main component which is a metal selected from tungsten, nickel, silver, platinum or gold. [0015]
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a cross sectional view showing a non-aqueous electrolyte cell and an electric double layer capacitor according to the invention. [0016]
  • FIG. 2 is a cross sectional view showing a non-aqueous electrolyte cell and an electric double layer capacitor according to the prior art. [0017]
  • DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • A typical construction according to the invention will be described with reference to FIG. 1. FIG. 1 is across sectional view showing a non-aqueous electrolyte cell or an electric double layer capacitor according to the invention. A concave-shaped container [0018] 101 of alumina is formed by applying tungsten printing on a green sheet to bake the same, and then applying wiring of a metallic layer of nickel or gold plating on the same. The container is manufactured by the same method as that for general ceramic packages for crystal oscillators. A metallic layer 109 serving as a first collector is provided on an entire inner bottom surface, and the metallic layer 109 extends through a wall surface of the concave-shaped container 101 to be electrically connected to a joining terminal A103 on an outer bottom surface of the concave-shaped container 101 via an outer side surface of the container. A similar metallic layer 110 is provided on an edge of a top surface of the concave-shaped container 101 to extend on a left side surface of the concave-shaped container shown in FIG. 1 to be electrically connected to a joining terminal B104 on the outer bottom surface of the concave-shaped container.
  • The joining terminals A, B may be provided on the outer bottom surface of the concave-shaped container [0019] 101, or extend on the side surface from an end on the bottom surface side of the concave-shaped container 101, and get wet on solder to be able to be soldered to a board.
  • A cathode active-material [0020] 106, a separator 105, and an anode active-material 107 are stackingly arranged and inserted on a top surface of the metallic layer 109, which defines a first collector on the inner bottom surface of the concave-shaped container 101, within the concave-shaped container 101, and a bonding material 108 is placed on the metallic layer 110 disposed on an edge of a top surface of the concave-shaped container 101. A sealing plate 102 of nickel is placed on the bonding material, and is pressurized and heated to melt the bonding material 108 for sealing.
  • The concave-shaped container [0021] 101 is preferably made of a heat resisting material such as heat resisting resins, glass, ceramics or ceramic glass or the like. A method of manufacturing the container can comprise using conductor printing to apply wiring on glass of low melting point and glass ceramics, and laminating and baking at low temperatures. Such wiring forms the joining terminal A103, the joining terminal B104, the metallic layer 109, which defines a first collector, and the metallic layer 110 disposed on the edge of the top surface of the concave-shaped container. A method of manufacturing that portion of the metallic layer 109, which extends through a wall surface of the concave-shaped container 101, is not limited to the above-mentioned method, but may comprise, for example, forming a board, which will make a bottom surface, and a frame-shaped member, which will make side surfaces of the concave-shaped container 101, forming the metallic layer 109 on the board, then stacking the board and the frame-shaped member on one another to bake them for uniting them, thus forming the concave-shaped container, whereby the portion of the metallic layer can extend through the container in gas-tight condition. Also, it is possible to perform wiring, stacking and baking with the use of conductor printing and a green sheet. In the case where the container is of a resin, the metallic terminals and the like can be formed by insert molding.
  • Also, that of the metallic layer [0022] 109, which makes a first collector of the wiring, is preferably of tungsten, silver and gold, which have good corrosion resistance and afford formation in the thick-film method. It is better to provide a layer of nickel, gold and solder on the joining terminals A103, B104 for soldering with the board. It is preferable to provide a layer of nickel, gold and the like, which are favorably compatible with the bonding material 108, on the metallic layer 110 on the edge of the concave-shaped container 101. Methods of forming such layers include plating, a gas phase method such as vapor deposition and the like.
  • The sealing plate [0023] 102 serves as a second collector and can be formed of a relatively many metals such as nickel, copper, brass, zinc, tin, gold, stainless steel, tungsten, aluminum and so on. This is because application of electric potential on a reduction side makes the metal hard to solve. On the other hand, since the metal must be made to solve when the sealing plate is used as a positive electrode, it is necessary that the material for the sealing plate be selected from a good anti-corrosion metal such as gold, platinum, stainless steel (SUS444, SUS239J4L, SUS317J4L, or the like) tungsten, aluminum and so on. In the case where a sealing plate is used which is formed of an insulating body such as heat resisting resins, glass, ceramics or ceramic glass or the like, it is necessary to provide a metallic layer, which will make a second collector, on an inner surface of the concave-shaped container 101. The material for the metallic layer can be of the same as that of the metallic sealing plate. Methods of forming the metallic layer include plating, a gas phase method such as vapor deposition, a printing method and the like.
  • The sealing plate [0024] 102 is connected to the joining terminal B104 through the bonding material 108, the metallic layer 110 and the like to serve as a second collector and a part of joining terminal. In the case of using the sealing plate of an insulating body, the metallic layer provided on the surface serves as a second collector and a part of the joining terminal.
  • That portion of the sealing plate [0025] 102, which contacts with the bonding material 108, is preferably provided with a layer such as nickel, gold which is well compatible with the bonding material 108.
  • The bonding material [0026] 108 includes brazing materials such as gold solder, silver solder or the like, and a solder material. In selecting the bonding material 108, it should take account of a material of the metallic layer 110 on the edge of the concave-shaped container 101, compatibility of the bonding material with a material of portions, through which the bonding material is joined to the sealing plate 102, and the reflow temperature. For example, in the case where the non-aqueous electrolyte cells and electric double layer capacitors according to the invention are mounted to the substrate at 240° C. by means of reflow, it is preferable to use a solder material, which melts at 300° C.
  • A way to seal the concave-shaped container [0027] 101 and the sealing plate 102 can make use of a technique such as thermo compression bonding, ultrasonic welding, resistance welding and so on, and is no particularly limitative. It is sufficient to select the best technique depending upon the materials of the concave-shaped container 101 and the sealing plate 102. In the case where resins are joined to each other or a resin and ceramics or metal are joined to each other, it is possible to make use of thermal melting and ultrasonic welding. In the case where ceramics are joined to each other or ceramics and metal are joined to each other, it is possible to perform thermal melting and ultrasonic welding with a resin interposed between the joining members or to make use of a bonding agent. To dip the joining members in a thermosetting resin after the sealing is effective in enhancing reliability.
  • In the case where the non-aqueous electrolyte cells and electric double layer capacitors according to the invention should be made small-sized, it is effective to form solder bumps on portions which make collectors serving as joining terminals. That is, it is effective to form them on the metallic layers on portions of the joining terminals A, B and the side surfaces of the container. Methods of forming solder bumps include plating, a gas phase method such as vapor deposition, a printing method, a micropressing method a ball bonding method and the like. [0028]
  • An insulating film having a large ion permeability and a predetermined mechanical strength is used to form the separator [0029] 105. In reflow soldering, it is possible to most stably use glass fiber and also to use a resin, such as polyphenylene sulfide, polyethylene terephthalate, polyamide, polyimide and so on, having the thermal deformation temperature of 230° C. or higher. Bore diameter and thickness of the separator are not specifically limitative, but are a matter of design determined on the basis of current value of a device, in which the non-aqueous electrolyte cells and electric double layer capacitors according to the invention are used, and the capacitor internal resistance. Also, it is possible to use porous ceramic bodies.
  • The electrolyte is not specifically limitative, and is a nonaqueous solvent used for conventional electric double layer capacitors and non-aqueous secondary batteries. The above-mentioned nonaqueous solvent includes cyclic ester kinds, linear ester kinds, cyclic ether kinds, linear ether kinds, and so on. [0030]
  • In the case where the electric double layer capacitors according to the invention are used for reflow soldering, a nonaqueous solvent having a boiling point of 200° C. or higher under normal pressure is stable as the electrolyte. The reflow temperature is in some cases as high as around 250° C., which is believed to be due to an increase in pressure within the battery at that temperature, and rupture of the battery did not occur even in the case where γ-butyrolactone (γBL) having a boiling point of 204° C. under normal pressure was used. It was favorable to use propylene carbonate (PC), ethylene carbonate (EC), γ-butyrolactone (γBL) separately or in composite. [0031]
  • As support salt, it is possible to use one or more of lithium salts such as (C[0032] 2H5) 4PBF4, (C3H7) 4PBF4, (CH3) (C2H5) 3NBF4, (C2H5 ) 4NBF4, (C2H5 ) 4PPF6, (C2H5) 4PCF3SO4, (C2H5) 4NPF4, lithium perchlorate (LiClO4), lithium phosphate hexafluoride (LiPF6), lithium fluoroborate (LiBF4), lithium arsenium hexafluoride (LiAsF6), trifluoromethane sulfonic acid lithium (LiCF3SO2), bistrifluoromethyl sulphonyl imide lithium [LiN(CF3SO2)2], thiocyanic salt, aluminum fluoride salt and so on.
  • In particular, it was effective to use polyethylene oxide derivatives or polymers containing the polyethylene oxide derivatives, polypropylene oxide derivatives or polymers containing the polypropylene oxide derivatives, phosphate ester polymers, PVDF or the like in combination with the above-mentioned nonaqueous solvent and the support salt in a gel state or solid state. While a large amount of the above-mentioned generated in some cases to interfere with sealing in the case where heat was applied in sealing the concave-shaped container [0033] 101 and the sealing plate 102 and in the case where a liquid electrolyte was used, sealing has been able to be simply carried out by the use of a gel or solid electrolyte.
  • Also, sealing is made further simple when an inorganic solid electrolyte of Li[0034] 2S/SiS2/Li4SiO4 is used.
  • Since the use of a gel or solid electrolyte can prevent inner short-circuiting due to lithium dendrite even when a lithium metal serves as a negative electrode, a lithium metal having a large capacity can be used as the anode active-material. [0035]
  • The non-aqueous electrolyte cells and electric double layer capacitors according to the invention are fundamentally free in configuration. A conventional electric double layer capacitor, in which sealing is achieved by caulking, as shown in FIG. 2 is limited to a substantially circular configuration. Therefore, when such conventional electric double layer capacitors are attempted to be arranged on the same substrate as that where other electronic parts, most of which are rectangular in configuration, are arranged, dead spaces are inevitably produced, resulting in spatial waste. The electric double layer capacitor according to the invention affords design in rectangular configuration, whereby it can be efficiently arranged on the substrate because of no lugs such as terminals and the like. [0036]
  • Embodiment 1
  • An electric double layer capacitor was manufactures by the use of a similar container to that shown in FIG. 1. The concave-shaped container [0037] 101 was made of alumina to have a size of 5×5×1 mm. A concave-shaped recess was 0.6 mm in depth and 5×5 mm in size. Wiring such as the joining terminal A103, joining terminal B104, the metallic layer 109, which made first collector, and the metallic layer 110 on the edge of the top surface of the concave-shaped container were provided by applying gold plating on tungsten. The concave-shaped container was prepared by using a nickel plate of 0.15 mm in thickness.
  • The active material was prepared by adding to 45 parts of a commercially available activated carbon (of 2260 m[0038] 2/g of specific surface area) 65 parts of carbon black as a conductive material, 40 parts of polyethylene oxide (PEO) as a gelling agent, 4 parts of (CH3) (C2H5) 3NBF4 as an electrolyte, and further 50 parts of a solution, which was obtained by dissolving 1 mol/L of (CH3)(C2H5) 3NBF4 into PC, and kneading them at 100° C. with a kneader (two-axle kneader). The material thus kneaded was milled with a rolling press to provide a sheet of 0.22 mm in thickness. Further, the sheet was dried at 100° C. until it was reduced by 15% in weight. The resulting sheet was cut into pieces of 3.6×3.6 mm to provide the cathode active-material 106 and the anode active-material 107.
  • Subsequently, 30 parts of a solution, which was obtained by dissolving 1 mol/L of (CH[0039] 3)(C2H5) 3NBF4 into PC, was added to 10 parts of PEO to be kneaded at 100° C. with a kneader (two-axle kneader). The material thus kneaded was interposed between nonwoven PPS clothes of 30 μm in thickness and milled with a rolling press to provide a sheet of 0.2 mm in thickness. The resulting sheet was cut into pieces of 4×4 μm to provide the separator 105.
  • The cathode active-material [0040] 106, the separator 105 and the anode active-material 107 were inserted in this order into the concave-shaped container 101, and an Au-based solder sheet of 80 μm in thickness, 5×5 mm in size and 0.5 mm in peripheral width, having the melting point of 320° C. was placed as the bonding material 108 on the edge of the concave-shaped container 101. Further, the sealing plate 102 of nickel was placed on the resulting product and pressurized by a flat copper plate having been heated to 340° C. for sealing.
  • Subsequently, a creamed solder was applied to portions on the substrate where the joining terminals were actually positioned, and the electric double layer capacitor thus manufactured was subjected to reflow soldering. The reflow soldering was carried out under the condition of preheating at 180° C. during 10 minutes and heating at 240° C. during 1 minute, with the result that there was caused no rupture or the like. [0041]
  • Embodiment 2
  • A non-aqueous electrolyte cell was manufactured by using the same concave-shaped container [0042] 101 as that in the embodiment 1.
  • A cathode active-material was prepared by adding to 50 parts of a commercially available MoO[0043] 3 35 parts of carbon black as a conductive material, 40 parts of polyethylene oxide (PEO) as a gelling agent, 4 parts of LiBF4 as an electrolyte, and further 20 parts of a solution, which was obtained by dissolving 1 mol/L of LiBF4 into γ-BL/EC (1:1), and kneading them at normal temperature with a kneader (two-axle kneader). The material thus kneaded was milled with a rolling press to provide a sheet of 0.21 mm in thickness. Further, the sheet was dried at 100° C. until it was reduced by 5% in weight. The resulting sheet was cut into pieces of 3.6×3.6 mm to provide the cathode active-material 106.
  • The anode active-material [0044] 107 was prepared by cutting a lithium sheet of 0.2 mm in thickness into pieces of 3.6×3.6 mm.
  • Subsequently, 30 parts of a solution, which was obtained by dissolving 1 mol/L of LiBF[0045] 4 into γ-BL/EC (1:1), was added to 10 parts of PEO to be kneaded at normal temperature with a kneader (two-axle kneader). The material thus kneaded was interposed between nonwoven PPS clothes of 30 μm in thickness and milled with a rolling press to provide a sheet of 0.2 mm in thickness. The resulting sheet was cut into pieces of 4×4 to provide the separator 105.
  • The cathode active-material [0046] 106, the separator 105 and the anode active-material 107 were inserted in this order into the concave-shaped container 101, and an Au-based solder sheet of 80 μm in thickness, 5×5 mm in size and 0.5 mm in peripheral width, having the melting point of 320° C. was placed as the bonding material 108 on the edge of the concave-shaped container 101. Further, the sealing plate 102 of nickel was placed on the resulting product and pressurized by a flat copper plate having been heated to 340° C. for sealing.
  • Subsequently, a creamed solder was applied to portions on the substrate where the joining terminals were actually positioned, and the non-aqueous electrolyte cell thus manufactured was subjected to reflow soldering. The reflow soldering was carried out under the condition of preheating at 180° C. during 10 minutes and heating at 240° C. during 1 minute, with the result that there was caused no rupture or the like. [0047]
  • It has been found that the constitution according to the invention can be subjected to reflow soldering in either non-aqueous electrolyte cells or electric double layer capacitors without any problem. [0048]
  • Embodiment 3
  • A non-aqueous electrolyte cell was manufactured by using an inorganic solid electrolyte for the separator [0049] 105 with the same constitution as that in the embodiment 2.
  • As the inorganic solid electrolyte, a lithium-ion conductive, crystallized glass was used which contained Li[0050] 2S/SiS2/Li4SiO4 and presented 10−3Scm−1 of ion conductivity. The glass was of 4×4×0.2 mm in size.
  • The cathode active-material [0051] 106, the solid electrolyte and the anode active-material 107 were inserted in this order into the concave-shaped container 101, and an Au-based solder sheet of 80 μm in thickness, 5×5 mm in size and 0.5 mm in peripheral width, having the melting point of 320° C. was placed as the bonding material 108 on the edge of the concave-shaped container 101. Further, the sealing plate 102 of nickel was placed on the resulting product and pressurized by a flat copper plate having been heated to 340° C. for sealing.
  • A creamed solder was applied to portions on the substrate where the joining terminals were actually positioned, and the non-aqueous electrolyte cell thus manufactured was subjected to reflow soldering. The reflow soldering was carried out under the condition of preheating at 180° C. during 10 minutes and heating at 240° C. during 1 minute, with the result that there was caused no rupture or the like. [0052]
  • Since the use of the inorganic solid electrolyte for the separator [0053] 105 eliminates short-circuiting, in which lithium dendrite generates on the negative electrode side lithium, reliability in cyclic life is markedly improved.
  • Embodiment 4
  • A non-aqueous electrolyte cell was manufactured by using Li[0054] 4Ti5O12 for the cathode active-material with the same constitution as that in the embodiment 3.
  • A cathode active-material was prepared by adding to 50 parts of a commercially available Li[0055] 4Ti5O12 35 parts of carbon black as a conductive material, 40 parts of polyethylene oxide (PEO) as a gelling agent, 4 parts of LiBF4 as an electrolyte, and further 20 parts of a solution, which was obtained by dissolving 1 mol/L of LiBF4 into γ-BL/EC (1:1), and kneading them at normal temperature with a kneader (two-axle kneader). The material thus kneaded was milled with a rolling press to provide a sheet of 0.21 mm in thickness. Further, the sheet was dried at 100° C. until it was reduced by 5% in weight. The resulting sheet was cut into pieces of 3.6×3.6 mm to provide the cathode active-material 106.
  • The cathode active-material [0056] 106, the solid electrolyte and the anode active-material 107 were inserted in this order into the concave-shaped container 101, and an Au-based solder sheet of 80 μm in thickness, 5×5 mm in size and 0.5 mm in peripheral width, having the melting point of 320° C. was placed on the edge of the concave-shaped container 101. Further, the sealing plate 102 of nickel was placed on the resulting product and pressurized by a flat copper plate having been heated to 340° C. for sealing.
  • The non-aqueous electrolyte cells thus manufactured involved no problem in reflow soldering. Since Li[0057] 4Ti5O12 was used as the cathode active-material 106, a cell resistant to overdischarge could be manufactured.
  • In the non-aqueous electrolyte cells and electric double layer capacitors according to the invention, reduction in a substrate-shaped space can be achieved since the joining terminals are made integral with the storage container and disposed in the lower portion of the container. Also, the non-aqueous electrolyte cells and electric double layer capacitors are made up of heat-resistant members to thereby afford reflow soldering. [0058]

Claims (12)

    What is claimed is:
  1. 1. A non-aqueous electrolyte cell having active materials used as a cathode and an anode, and a container for receiving the materials and an electrolyte, comprising
    the container is composed of a concave-shaped container and a sealing plate, and the concave-shaped container is provided on an inner bottom surface thereof with a first collector, which is electrically connected to a joining terminal A disposed on an outer bottom surface and/or sides of the concave-shaped container, the sealing plate being provided on a surface inside the cell with a second collector, which is electrically connected to a joining terminal B disposed on an outer bottom surface and/or sides of the concave-shaped container.
  2. 2. The non-aqueous electrolyte cell according to
    claim 1
    , wherein the concave-shaped container of the receiving container is selected from heat resisting resins, glass, ceramics or ceramic glass, and the first collector is provided on the inner bottom surface of the concave-shaped container and electrically connected to a joining terminal A disposed on the outer bottom surface of the concave-shaped container, the concave-shaped container being formed on an edge thereof with a metallic layer, which is electrically connected to a joining terminal B disposed on the outer bottom surface of the concave-shaped container, and wherein a sealing surface on a top of the concave-shaped container is sealed by the sealing plate, which has a metallic portion serving as the second collector and the joining terminal.
  3. 3. The non-aqueous electrolyte cell and an electric double layer capacitor according to
    claim 1
    , wherein the first collector and the joining terminals disposed on the concave-shaped container of the receiving container and the metallic layer on the edge of the container are composed of a material having a main component which is a metal selected from tungsten, nickel, silver, platinum or gold.
  4. 4. The non-aqueous electrolyte cell according to
    claim 1
    , wherein surfaces on those portions of the joining terminals, which are exposed outside the receiving container, are provided with nickel, gold or solder.
  5. 5. The non-aqueous electrolyte cell according to
    claim 2
    wherein the concave-shaped container and the sealing plate are sealed by interposing a brazing material or a solder material between the concave-shaped container and the sealing plate and heating them.
  6. 6. The non-aqueous electrolyte cell according to
    claim 1
    , wherein the electrolyte is solid or gel.
  7. 7. An electric double layer capacitor having active materials used as a cathode and an anode, and a container for receiving the materials and an electrolyte, comprising
    the container is composed of a concave-shaped container and a sealing plate, and the concave-shaped container is provided on an inner bottom surface thereof with a first collector, which is electrically connected to a joining terminal A disposed on an outer bottom surface and/or sides of the concave-shaped container, the sealing plate being provided on a surface inside the cell with a second collector, which is electrically connected to a joining terminal B disposed on an outer bottom surface and/or sides of the concave-shaped container.
  8. 8. The electric double layer capacitor according to
    claim 1
    , wherein the concave-shaped container of the receiving container is selected from heat resisting resins, glass, ceramics or ceramic glass, and the first collector is provided on the inner bottom surface of the concave-shaped container and electrically connected to a joining terminal A disposed on the outer bottom surface of the concave-shaped container, the concave-shaped container being formed on an edge thereof with a metallic layer, which is electrically connected to a joining terminal B disposed on the outer bottom surface of the concave-shaped container, and wherein a sealing surface on a top of the concave-shaped container is sealed by the sealing plate, which has a metallic portion serving as the second collector and the joining terminal.
  9. 9. The electric double layer capacitor according to
    claim 1
    , wherein the first collector and the joining terminals disposed on the concave-shaped container of the receiving container and the metallic layer on the edge of the container are composed of a material having a main component which is a metal selected from tungsten, nickel, silver, platinum or gold.
  10. 10. The electric double layer capacitor according to
    claim 1
    , wherein surfaces on those portions of the joining terminals, which are exposed outside the receiving container, are provided with nickel, gold or solder.
  11. 11. The electric double layer capacitor according to
    claim 2
    wherein the concave-shaped container and the sealing plate are sealed by interposing a brazing material or a solder material between the concave-shaped container and the sealing plate and heating them.
  12. 12. The electric double layer capacitor according to
    claim 1
    , wherein the electrolyte is solid or gel.
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JP2000027730A JP3959220B2 (en) 2000-02-04 2000-02-04 Non-aqueous surface-mount electrolytic cell and surface mount for an electric double layer capacitor

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