WO2023119765A1 - 電気化学デバイスおよびその製造方法 - Google Patents

電気化学デバイスおよびその製造方法 Download PDF

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Publication number
WO2023119765A1
WO2023119765A1 PCT/JP2022/035255 JP2022035255W WO2023119765A1 WO 2023119765 A1 WO2023119765 A1 WO 2023119765A1 JP 2022035255 W JP2022035255 W JP 2022035255W WO 2023119765 A1 WO2023119765 A1 WO 2023119765A1
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Prior art keywords
gasket
outer peripheral
peripheral side
electrochemical device
cylindrical
Prior art date
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Ceased
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PCT/JP2022/035255
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English (en)
French (fr)
Japanese (ja)
Inventor
照久 三浦
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to US18/718,526 priority Critical patent/US20250046923A1/en
Priority to CN202280082432.4A priority patent/CN118382958A/zh
Priority to JP2023569069A priority patent/JP7664533B2/ja
Publication of WO2023119765A1 publication Critical patent/WO2023119765A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/184—Sealing members characterised by their shape or structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H01M50/148—Lids or covers characterised by their shape
    • H01M50/152—Lids or covers characterised by their shape for cells having curved cross-section, e.g. round or elliptic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H01M50/155—Lids or covers characterised by the material
    • H01M50/16—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H01M50/155—Lids or covers characterised by the material
    • H01M50/164—Lids or covers characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H01M50/166—Lids or covers characterised by the methods of assembling casings with lids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H01M50/166—Lids or covers characterised by the methods of assembling casings with lids
    • H01M50/171—Lids or covers characterised by the methods of assembling casings with lids using adhesives or sealing agents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to an electrochemical device and its manufacturing method.
  • Patent Document 1 discloses a positive electrode case containing a cylindrical positive electrode active material, a negative electrode collector rod in which lithium and a separator are wound, and an organic electrolyte. are respectively inserted and injected, and a gasket is inserted into the opening of the case, and a hole is provided in the center that is 0.1 to 0.3 mm smaller than the outer diameter of the collector rod, and is 0.1 to 0.0 mm smaller than the inner diameter of the case.
  • a narrow lithium battery having an outer diameter smaller by 3 mm and sealed with a rubber-elastic cylindrical gasket is disclosed.
  • the cylindrical gasket shown in Patent Document 1 is formed by, for example, compression molding a sheet integrally formed with a plurality of gaskets arranged two-dimensionally and connecting portions continuous with each of the plurality of gaskets.
  • Manufactured by A plurality of gaskets in the sheet are singulated by punching out the formed sheet and separating the gaskets from the joints.
  • the connecting portion located around the outer peripheral side surface of the cylindrical gasket is thinned. The punching pulls and breaks the thinned connection, separating the gasket from the sheet.
  • a fractured portion is formed on the outer peripheral side surface of the cylindrical gasket due to the tensile force.
  • the broken portion has a rougher surface than other portions, and a protruding portion protruding from the outer peripheral side surface may be formed as a burr in the broken portion.
  • An electrochemical device includes an electrode group including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, and an opening, which accommodates the electrode group. and a gasket for sealing an opening of the cylindrical case.
  • the gasket has a cylindrical shape having a through hole extending along the axis, and has an outer peripheral side surface extending in the axial direction along the axis and a first bottom surface coupled to one end of the outer peripheral side surface and having one end of the through hole open. and a second bottom surface coupled to the other end of the outer peripheral side surface and opening the other end of the through hole.
  • the first bottom surface of the tubular shape is continuous with the outer peripheral side surface of the tubular shape via a tapered surface that is inclined with respect to the outer peripheral side surface.
  • a portion of the gasket along the outer peripheral side surface is compressed by reducing the diameter of a portion of the outer periphery of the cylindrical case to form a compressed portion.
  • At least a partial region of the tapered surface is a rough surface having surface roughness larger than that of the outer peripheral side surface of the compression portion.
  • the cylindrical shape has a through hole, and the bottom surface where one end of the cylindrical through hole opens is composed of the outer peripheral side surface of the cylindrical shape and the To obtain a gasket continuous via a tapered surface inclined to an outer peripheral side surface.
  • a cylindrical case having an opening and a bottom is prepared.
  • An electrode group having a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, and an electrolyte are accommodated in the cylindrical case, and the bottom surface of the gasket faces the electrode group.
  • the gasket is inserted into the opening of the tubular case so as to seal the opening of the tubular case.
  • a molded sheet provided with a connection portion having a surface continuous with the bottom surface, wherein a plurality of gaskets including the gasket are arranged one-dimensionally or two-dimensionally so as to be connected via the connection portion.
  • the connecting portion is broken so that a broken surface inclined with respect to the outer peripheral side surface is formed, and the gasket is separated from the molded sheet.
  • FIG. 1 is a side view and a bottom view schematically showing an example of the configuration of a gasket used in an electrochemical device according to one embodiment of the present disclosure.
  • 2 is a cross-sectional view schematically showing an example of a molded sheet for manufacturing the gasket shown in FIG. 1.
  • FIG. 3 is a side view schematically showing another example of the configuration of the gasket used in the electrochemical device according to one embodiment of the present disclosure.
  • FIG. 4 is a partial cross-sectional front view of an electrochemical device according to an embodiment of the present disclosure.
  • An electrochemical device includes an electrode group having a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode; and a bottomed cylindrical case that houses the electrode group. and a gasket that seals the opening of the tubular case.
  • an electrochemical device is a concept that includes batteries such as lithium ion secondary batteries and lithium primary batteries, and capacitors such as lithium ion capacitors and electric double layer capacitors.
  • the positive and negative electrodes of an electrochemical device may each be polarizable or non-polarizable electrodes.
  • the positive electrode and/or the negative electrode may be, for example, a polarizable electrode that develops capacity by forming an electric double layer through adsorption of ions to the active material.
  • the positive electrode and/or the negative electrode may be, for example, a non-polarizable electrode that develops capacity as a result of the Faraday reaction in which lithium ions are reversibly absorbed and discharged.
  • the electrochemical device may exhibit capacity through absorption and/or release of lithium ions, or may exhibit capacity through adsorption/desorption or chemical interaction of lithium ions with an active material. .
  • the gasket has a cylindrical shape with a through hole extending along the axis, and has an outer peripheral side surface and two bottom surfaces facing each other via the outer peripheral side surface and the tapered surface.
  • One first bottom surface of the cylindrical shape is continuous with the outer peripheral side surface of the cylindrical shape through a tapered surface that is inclined with respect to the outer peripheral side surface.
  • a part along the outer peripheral side surface of the gasket is compressed by reducing the diameter of part of the outer periphery of the cylindrical case to form a compressed portion.
  • the repulsive force of the gasket in the compressed portion ensures sealing between the gasket and the tubular case.
  • At least a partial area of the tapered surface is a rough surface having a larger surface roughness than the outer peripheral side surface of the compressed portion.
  • the area on the tapered surface that is rougher than the outer peripheral side surface is formed, for example, by singulating the gaskets by, for example, punching from a molded sheet in which a plurality of gaskets are arranged one-dimensionally or two-dimensionally. Includes fracture surface.
  • a fracture surface is formed by applying a tensile stress to a connecting portion connecting a plurality of gaskets to break the connecting portion.
  • a fracture surface may be formed in the tapered surface by cutting the connecting portion.
  • the second bottom surface of the other may be continuous with the outer peripheral side surface of the tubular shape via a second tapered surface that is inclined with respect to the outer peripheral side surface.
  • One of the first bottom surfaces and/or the other of the second bottom surfaces may be provided with an annular protruding portion extending so as to surround the through hole and/or an uneven surface. The functions of the second tapered surface, the projecting portion, and the uneven surface will be described later.
  • the tapered surface of the gasket is configured to form a fractured surface. is prevented from interfering with the inner surface of the case.
  • the tubular case can be easily sealed with a gasket, and productivity is dramatically improved.
  • the gasket can be inserted and fixed at a desired position with high accuracy, the sealing performance of the gasket can be maintained at a high level, and the reliability of the electrochemical device can be maintained at a high level.
  • FIG. 1 is a diagram schematically showing an example of the configuration of a gasket 13 used in an electrochemical device according to one embodiment of the present disclosure.
  • the side view of FIG. 1 is a side view of the gasket 13, and the bottom view of FIG.
  • the gasket 13 shown in FIG. 1 has a cylindrical shape with a through hole 13h extending along the axis 13p in the central portion. 13 h of through-holes are closed with the current collection rod 14 (refer FIG. 4).
  • the collector rod functions as an external terminal by being inserted into the through hole 13h so that one end thereof is exposed to the outside.
  • the shaft 13p extends in the axial direction D13.
  • the gasket 13 has cylindrical bottom surfaces 13a and 13b and an outer peripheral side surface 13c connecting the bottom surfaces 13a and 13b.
  • the bottom surface 13a is continuous with the outer peripheral side surface 13c via the tapered surface 13d.
  • At least a partial region 13X of the tapered surface 13d is a fractured surface 13k formed by breaking the gasket from the molded sheet, and is wider than the outer peripheral side surface 13c of the compressed portion 13f in contact with the reduced diameter portion 35 (see FIG. 4). It has a large surface roughness (arithmetic mean roughness).
  • the bottom surface 13a is coupled to one end 13ca of the outer peripheral side surface 13c in the axial direction D13, and one end 13ha of the through hole 13h opens.
  • the bottom surface 13b is coupled to the other end 13cb of the outer peripheral side surface 13c in the axial direction D13, and the other end 13hb of the through hole 13h opens.
  • the bottom surface 13b of the gasket 13 is provided with an annular projecting portion 131 extending so as to surround the through hole 13h.
  • the outer peripheral surface of the annular protruding portion 131 is tapered with respect to the bottom surface 13b, but the outer peripheral surface of the protruding portion 131 may be perpendicular to the bottom surface 13b.
  • FIG. 2 is a cross-sectional view schematically showing an example of the formed sheet 100 before the gasket 13 shown in FIG. 1 is singulated.
  • the molded sheet 100 has a structure in which a plurality of gaskets 13 are connected one-dimensionally or two-dimensionally via connecting portions 102, and the plurality of gaskets 13 and connecting portions 102 are formed as a whole. forming a sheet.
  • the molded sheet 100 is manufactured, for example, by compression molding.
  • the connecting portion 102 is plate-like or film-like having two main surfaces 102a and 102b opposite to each other. However, the connecting portion 102 does not have to completely fill the space between the plurality of gaskets 13 , and the formed sheet 100 has a region (for example, a through hole) that is not filled with the plurality of gaskets 13 or the connecting portion 102 . may be formed.
  • One main surface 102 a of the connecting portion 102 is continuous with the bottom surface 13 a of the gasket 13 .
  • the other main surface 102b of the connecting portion 102 is continuous with the end portion of the outer peripheral side surface 13c of the gasket 13 on the side of the bottom surface 13a.
  • the connecting part 102 receives tensile stress and breaks, punching the gasket 13 from the molded sheet 100, and separating the gasket 13. be done. At this time, by punching so as to form a fractured surface 13k inclined with respect to the bottom surface 13a and the outer peripheral side surface 13c, the gasket 13 having a cross section on a part of the tapered surface 13d is obtained.
  • the surface roughness (arithmetic mean roughness) Ra of the outer peripheral side surface 13c of the compressed portion 13f that contacts the diameter-reduced portion 35 (see FIG. 4) is, for example, 0.006 mm or less.
  • the surface roughness (arithmetic mean roughness) Ra of the tapered surface 13d, which is the fracture surface 13k is, for example, greater than 0.006 mm, and may be 0.009 mm or more or 0.015 mm or more.
  • the direction from one cylindrical bottom surface 13a to the other bottom surface 13b is an axial direction D13 along the axis 13p.
  • h1 be the maximum height of the tapered surface 13d in the axial direction D13 with reference to one bottom surface 13a of the cylindrical shape.
  • h2 be the height from one bottom surface 13a of the cylinder to the end 13cb on the other bottom surface 13b side of the outer peripheral side surface 13c in the axial direction D13.
  • the ratio h1/h2 of height h1 to height h2 may be in the range of 0.04 to 0.43. If the ratio h1/h2 is 0.04 or more, the connecting portion 102 of the molded sheet 100 can be made sufficiently thick, the molded sheet 100 can be easily separated from the molding die, and productivity is improved.
  • the tapered surface of the gasket does not overlap the diameter-reduced portion of the tubular case 11, making it easy to maintain stable sealing performance.
  • the height h2 considers the height of the second tapered surface when a second tapered surface, which will be described later, is formed between the bottom surface 13b and the outer peripheral side surface 13c.
  • the ratio h2/R of the height h2 to the outer diameter (diameter) R of the outer peripheral side surface 13c may be 0.18 or more and 1.6 or less, or may be 0.23 or more and 1.6 or less.
  • the smaller the ratio h2/R the smaller the thickness of the gasket (the height in the axial direction D13) relative to the outer diameter R, and the smaller the volume occupied by the gasket with respect to the cylindrical case 11.
  • a high capacity can be easily realized by increasing the amount of the enclosed material and the amount of the electrode active material.
  • the larger the ratio h2/R the more the sealability of the gasket can be improved, the higher the sealing withstand voltage, and the higher the reliability of the electrochemical device.
  • the ratio h2/R is in the range of 0.18 or more and 1.6 or less, it is easy to achieve both high capacity and high reliability due to the high sealing performance of the gasket.
  • the pressure inside the cylindrical case may increase. If the gasket bulges to a certain extent or more due to an increase in internal pressure, the repulsive force applied from the gasket to the inner surface of the cylindrical case may decrease, and the sealing performance may deteriorate. Therefore, it is preferable that the gasket has a structure capable of suppressing swelling due to an increase in internal pressure, or is made of a material capable of suppressing swelling. In general, the larger the ratio h2/R, the better, from the viewpoint of suppressing swelling of the gasket against an increase in internal pressure.
  • the allowable width of the height position of the diameter-reduced portion can be increased, so that the productivity of the product can be improved.
  • a gasket having a ratio h2/R of 1.6 or less it is possible to obtain sufficient deformation resistance against internal pressure under normal use conditions.
  • the gasket when a rubber material is used for the gasket, using a rubber material such as butyl rubber for the gasket provides a stable sealing repulsion force and improves sealing performance.
  • rubber materials are prone to deformation due to increased internal pressure.
  • the ratio h2/R is less than 0.23, the use of a rubber material having a Young's modulus of about 0.05 GPa or less may result in insufficient rigidity from the viewpoint of suppression of swelling.
  • the gasket may have a laminated structure having at least two layers, a rubber material layer (for example, a butyl rubber layer) and a fluororesin layer.
  • the Young's modulus of the fluororesin may be 0.4 GPa or more as a general value.
  • the height h2 of the gasket is 1.2 mm and the outer diameter R is 6.6 mm (unloaded state).
  • a gasket with a ratio h2/R of 0.18 can be used.
  • the height of the fluororesin layer is, for example, 0.7 mm
  • the height of the rubber material layer is, for example, 0.5 mm
  • the height of the gasket can be reduced to less than 1.5 mm.
  • the space inside the case excluding the amount of the electrolyte and the amount of the electrode active material can be increased, reflow resistance can be improved and the characteristics can be maintained for a longer period of time.
  • the outer diameter of the gasket may be larger than the outer diameter (diameter) of the cylindrical case.
  • the gasket is press-fitted into the tubular case to improve the adhesion between the outer surface of the fluororesin layer portion of the gasket and the inner surface of the case.
  • the adhesion between the rubber material layer of the same diameter as the fluororesin layer and the inner surface of the case is enhanced, and when the gasket is inserted into the case, it prevents electrolyte from flowing out from the gap between the inner surface of the case and the outer surface of the gasket. prevent it and improve productivity.
  • the amount of diameter reduction when forming the diameter-reduced portion in the cylindrical case can be reduced.
  • the tapered surface 13d is formed in the rubber material layer. Also, the compressed portion 13f that contacts the diameter-reduced portion 35 (see FIG. 4) of the cylindrical case is formed in the rubber material layer.
  • the ratio h2/R is 0.23 or more, even if the gasket 13 is made of a single rubber material, it can retain deformation resistance against internal pressure.
  • a chemical device can be provided.
  • the taper angle ⁇ 1 of the tapered surface 13d is, for example, 4.6° or more and less than 90°.
  • ⁇ 1 is 4.6° or more
  • the burr formed on the fracture surface 13k protrudes from the outer peripheral side 13c, and when the gasket is inserted into the opening of the cylindrical case, the burr interferes with the inner side of the case. can be sufficiently suppressed.
  • the angle ⁇ 2 formed between the tapered surface 13d and the outer peripheral side surface 13c (axial direction D13) may be, for example, 2.3° or more and 45° or less.
  • the bottom surface 13b of the gasket 13 is provided with an annular projecting portion 131 extending so as to surround the through hole 13h.
  • the protruding portion 131 is provided on the bottom surface of the gasket 13 that does not face the electrode group (that is, the bottom surface on the side opposite to the tapered surface 13d across the outer peripheral side surface 13c), and penetrates through water droplets or the like adhering to the bottom surface. It has the function of suppressing the occurrence of leakage current between the collector rod that closes the hole 13h and the cylindrical case.
  • the gasket 23 is locally compressed by providing a portion of the outer circumference of the cylindrical case 11 with a reduced diameter portion 35, thereby sealing the opening of the cylindrical case 11. Also, a curled portion 31 is formed at the end of the cylindrical case 11 on the opening side (see FIG. 4). At this time, if the bottom surface 13b on the side that does not face the electrode group is a flat surface, a step is formed between the bottom surface 13b and the curled portion 31 formed along the bottom surface 13b, and a recess 13t can be formed in the bottom surface 13b. .
  • the collector rod end portion 32 and the curled portion 31 of the cylindrical case 11 may be short-circuited via the water droplets or the like, causing leakage current to flow.
  • the protruding portion 131 on the bottom surface 13b, even when the curled portion is formed at the end of the cylindrical case 11 opening side, the current collector rod end portion 32 and the curled portion 31 of the cylindrical case 11 are not separated. It is possible to suppress current leakage through water droplets or the like in between.
  • the outer diameter of the projecting surface of the annular projecting portion 131 is, for example, 0.39 times or more and 0.86 times or less as large as the outside diameter R of the outer peripheral side surface 13c.
  • R the outer diameter of the protruding surface
  • a sufficient thickness of the protruding portion 131 can be secured in the radial direction, and molding is easy.
  • the gasket position can be maintained at a high level against the internal pressure of the cylindrical case during normal use, and high sealing reliability can be achieved.
  • the projecting portion 131 suppresses current leakage between the collector rod end portion 32 and the curled portion 31 of the cylindrical case 11 . Therefore, by extending the curled portion 31 inward toward the outer peripheral side surface of the projecting portion 131, the opening ratio obtained by dividing the inner diameter of the tip of the curled portion by the outer diameter of the case can be reduced. As a result, intrusion of moisture from the outside can be suppressed, and long-term reliability of the electrochemical device can be improved. Also, swelling of the gasket on the case opening surface of the product during reflow can be suppressed.
  • the gasket can be easily formed and productivity can be maintained high.
  • the radial thickness of 131 is preferably 0.2 mm or more. Therefore, in this case, the outer diameter (diameter) of the protruding surface of the protruding portion 131 is preferably 1.4 mm or more, and is preferably 0.39 times or more the outer diameter R of the outer peripheral side surface 13c.
  • the outer peripheral side surface of the annular projecting portion 131 may be perpendicular to the bottom surface 13b, but as shown in FIG. A tapered shape with a smaller diameter is more preferable.
  • the molded sheet 100 shown in FIG. 2 is formed by compression molding, and the releasability is improved when the molded sheet 100 is removed from the molding die. can be provided.
  • At least one of the bottom surfaces of the cylindrical gasket may have an uneven surface or a satin finish.
  • the bottom surface 13a of the gasket 13 is formed with a concentric uneven surface 132 around the through hole 13h.
  • the gasket 13 normally has stickiness.
  • the uneven surface 132 reduces the contact area and prevents the gaskets 13 from sticking together even when the gaskets 13 are put into a feeder for sealing the cylindrical case and the gaskets 13 come into contact with each other in the feeder. be. This facilitates the handling of the gasket and dramatically improves productivity.
  • the uneven surface 132 may be formed on the bottom surface 13b.
  • the protruding surface of the protruding portion 131 may be the uneven surface 132 .
  • the uneven surface 132 can have the function of limiting the fracture position where the tapered surface 13 d is formed by punching the molded sheet 100 to the position of the concave portion of the uneven surface 132 .
  • the tapered surface 13 d is formed so as to be continuous with the recessed portion of the uneven surface 132 .
  • the height of the center of gravity of the gasket 23 from the bottom surface 13a in the axial direction D13 is 0.45 ⁇ H to 0.498 ⁇ H with respect to the maximum distance H between one bottom surface 13a and the other bottom surface 13b of the gasket 13. may be located within the range of In this case, the application of vibration of a specific frequency causes a difference in amplitude induced between the bottom surface 13a and the bottom surface 13b. direction) can be controlled, and productivity is dramatically improved. More preferably, the height of the center of gravity of the gasket 23 from the bottom surface 13a is in the range of 0.46 ⁇ H to 0.49 ⁇ H.
  • the maximum distance H, maximum height h1 and height h2 of the gasket 23 are the dimensions of the gasket 23 in an unloaded state where the gasket is removed from the electrochemical device and not inserted into the cylindrical case 11. .
  • the maximum distance H is the height in consideration of the protruding portion 131 and the uneven surface 132 when the protruding portion 131 is provided on the bottom surface 13b and/or when the uneven surface 132 is provided on the bottom surface 13a. Satoru. That is, the maximum distance H is the maximum height of the gasket 13 from the reference plane when the gasket 13 is arranged on the reference plane so that the bottom surface 13a faces downward.
  • the projecting portion 131 when the projecting portion 131 is provided on the bottom surface 13a, when the gasket 13 is placed on the reference surface so that the bottom surface 13a faces downward, the height h1 and h2 are respectively equal to the reference surface. From the maximum height of the tapered surface 13d from and the height of the outer peripheral side surface 13c from the reference surface (the height of the second tapered surface 13e from the reference surface when the second tapered surface 13e is provided), the projecting portion 131 Subtract the height of The height h2 means the distance from one bottom surface 13a to the other bottom surface 13b.
  • the gasket 13 By providing the tapered surface 13d, the gasket 13 normally moves the center of gravity toward the bottom surface 13b. In order to position the center of gravity of the gasket at a position of 0.45 ⁇ H to 0.498 ⁇ H from the bottom surface 13a, for example, the projecting portion 131 is provided on the bottom surface 13b.
  • the gasket 13 may have a multi-layer structure in which a plurality of materials are laminated in the axial direction D13 of the gasket 13, and a layer of a higher density material among the plurality of materials may be arranged on the bottom surface 13a.
  • another tapered surface may be provided on the bottom surface 13b. That is, the other bottom surface of the cylindrical gasket may be continuous with the cylindrical outer peripheral side surface and the outer peripheral side surface via a second tapered surface that is inclined with respect to the outer peripheral side surface.
  • the second tapered surface is formed at an arbitrary inclination angle according to the mold used during molding. Therefore, the surface roughness of the second tapered surface is the same as the surface roughness of the outer peripheral side surface of the reduced diameter portion.
  • FIG. 3 is a schematic side view showing an example of a gasket 23 provided with a second tapered surface 13e continuous with the bottom surface 13b and the outer peripheral side surface 13c.
  • the gasket 23 is provided with an annular projecting portion 131 extending so as to surround the through hole 13h on both the bottom surface 13a and the bottom surface 13b.
  • An uneven surface or a satin finish may be provided on the projecting surface of the projecting portion 131 .
  • the angle between the second tapered surface 13e and the outer peripheral side surface 13c is substantially the same as the angle ⁇ 2 between the tapered surface 13d and the outer peripheral side surface 13c.
  • the heights of the two projecting portions 131 provided on the bottom surface 13a and the bottom surface 13b are also substantially the same.
  • the overall shape of the gasket 13 is symmetrical with respect to the surface 13s perpendicular to the cylindrical axis 13p (except that the tapered surface 13d and the second tapered surface 13e have different surface roughnesses). ing.
  • the gasket 23 when conveying the gasket 23 to the opening end of the cylindrical case 11, it is not necessary to align the direction of the gasket 23.
  • the gasket 23 may be transported with the bottom surface 13a facing upward, or may be transported with the bottom surface 13b facing upward.
  • the gasket 23 may be inserted into the tubular case 11 so that the bottom surface 13a faces the electrode group, or the gasket 23 may be inserted into the tubular case so that the bottom surface 13b faces the electrode group. In either case, the gasket can be accurately inserted and fixed into the open end of the cylindrical case, and the same sealing performance can be obtained, thereby improving productivity.
  • the structure of the electrochemical device may be a wound electrode group configured by spirally winding a strip-shaped positive electrode and a strip-shaped negative electrode with a separator interposed therebetween.
  • a single-layer or laminated electrode group in which a negative electrode is laminated via a separator may be provided. Note that when the configuration of the present disclosure is applied to a cylindrical electrochemical device, the outer diameter-to-height ratio does not matter.
  • One of the positive electrode and the negative electrode in the electrode group is electrically connected to a collector rod, which is a collector having a bar or rod shape.
  • the collector bar closes the through-hole of the gasket, and one end of the collector bar is exposed to the outside.
  • One end of the collector rod exposed to the outside functions as an external terminal.
  • the other of the positive electrode and the negative electrode in the electrode group may be electrically connected to the cylindrical case.
  • one of the collector rod and the cylindrical case constitutes a positive electrode external terminal, and the other constitutes a negative electrode external terminal.
  • a plurality of (for example, two) through holes may be provided in the gasket.
  • the same number of current collector rods as the through holes are provided.
  • Each of the plurality of current collector rods closes the corresponding through hole of the gasket and has one end exposed to the outside.
  • one or more current collecting rods are electrically connected to one of the positive electrode and the negative electrode in the electrode group, and one or more other current collecting rods are electrically connected to the other of the positive electrode and the negative electrode in the electrode group. be done.
  • one or more collector rods electrically connected to the positive electrode constitute a positive electrode external terminal
  • one or more collector rods electrically connected to the negative electrode constitute a positive electrode external terminal. do.
  • a method for manufacturing an electrochemical device has a cylindrical shape having a through hole in the center, and one first bottom surface of the cylindrical shape is the outer peripheral side surface of the cylindrical shape and the outer peripheral side surface.
  • Step (i) of obtaining a gasket continuous via an inclined tapered surface Step (ii) of preparing a cylindrical case with a bottom, a positive electrode, a negative electrode, and a With the electrode group having the separator and the electrolyte housed in the cylindrical case, the gasket is inserted into the opening of the cylindrical case so that the first bottom surface faces the electrode group, and the opening of the cylindrical case It has a step (iii) of sealing the part.
  • the step (ii) for obtaining a gasket includes forming a formed sheet having a connection portion having a surface continuous with the first bottom surface, and having a plurality of the gaskets arranged one-dimensionally or two-dimensionally so as to be connected via the connection portion. and separating the gasket from the molded sheet by breaking the connecting portion so that a fracture surface 13k inclined with respect to the outer peripheral side surface is formed.
  • the positive electrode can include a positive electrode mixture layer (positive electrode active material layer) and a positive electrode current collector that holds the positive electrode mixture layer.
  • the positive electrode mixture layer contains a positive electrode active material and, if necessary, a conductive agent, a binder, and the like.
  • the positive electrode current collector is, for example, metal foil, and is formed into a belt shape suitable for winding. Although the material of the positive electrode current collector is not limited to this, examples thereof include aluminum and aluminum alloys.
  • the positive electrode current collector may contain expanded metal.
  • the expanded metal mesh is filled with a positive electrode mixture in a wet state prepared by adding a positive electrode active material, an additive such as a conductive material and a binder, and an appropriate amount of water. can be obtained by applying pressure in the thickness direction and drying.
  • Manganese dioxide is mentioned as a positive electrode active material contained in the positive electrode.
  • a positive electrode containing manganese dioxide develops a relatively high voltage and has excellent pulse discharge characteristics.
  • Manganese dioxide may be in a mixed crystal state containing a plurality of crystal states.
  • the positive electrode may contain manganese oxides other than manganese dioxide.
  • Manganese oxides other than manganese dioxide include MnO, Mn 3 O 4 , Mn 2 O 3 and Mn 2 O 7 . It is preferable that the main component of the manganese oxide contained in the positive electrode is manganese dioxide.
  • Part of the manganese dioxide contained in the positive electrode may be doped with lithium. If the doping amount of lithium is small, a high capacity can be secured.
  • Manganese dioxide and manganese dioxide doped with a small amount of lithium can be represented by LixMnO 2 (0 ⁇ x ⁇ 0.05).
  • the average composition of all manganese oxides contained in the positive electrode should be LixMnO 2 (0 ⁇ x ⁇ 0.05).
  • the ratio x of Li should be 0.05 or less in the initial state of discharge of the lithium primary battery.
  • the ratio x of Li generally increases as the discharge of the lithium primary battery progresses.
  • the oxidation number of manganese contained in manganese dioxide is theoretically tetravalent.
  • the oxidation number of manganese may decrease from 4. Therefore, in LixMnO 2 , the average oxidation number of manganese is allowed to be slightly smaller than tetravalent.
  • the positive electrode can contain other positive electrode active materials used in lithium primary batteries. Fluorinated graphite etc. are mentioned as another positive electrode active material. The proportion of LixMnO 2 in the entire positive electrode active material may be 90% by mass or more.
  • Electrolytic manganese dioxide is preferably used as manganese dioxide. If necessary, electrolytic manganese dioxide that has been subjected to at least one of neutralization treatment, washing treatment, and calcination treatment may be used. Electrolytic manganese dioxide is generally obtained by electrolysis of an aqueous manganese sulfate solution.
  • the positive electrode may be other positive electrode active materials used in lithium primary batteries.
  • the positive electrode when the positive electrode is composed of graphite fluoride, it is possible to maintain performance at higher temperatures, and lithium primary batteries with excellent long-term reliability. can be realized.
  • binders examples include fluororesins, rubber particles, and acrylic resins.
  • Examples of conductive agents include conductive carbon materials.
  • Examples of conductive carbon materials include natural graphite, artificial graphite, carbon black, and carbon fiber.
  • the negative electrode may contain metallic lithium, a lithium alloy, or both metallic lithium and a lithium alloy.
  • a composite containing metallic lithium and a lithium alloy may be used for the negative electrode.
  • Lithium alloys include Li--Al alloys, Li--Sn alloys, Li--Ni--Si alloys, and Li--Pb alloys.
  • the content of metal elements other than lithium contained in the lithium alloy is preferably 0.05 to 15% by mass from the viewpoint of securing discharge capacity and stabilizing internal resistance.
  • Metallic lithium, lithium alloys, or composites thereof can be formed into any shape and thickness according to the shape, dimensions, standard performance, etc. of the lithium primary battery.
  • a sheet of metallic lithium, a lithium alloy, or a composite thereof may be used for the negative electrode. Sheets are obtained, for example, by extrusion. More specifically, a cylindrical battery uses a metallic lithium or lithium alloy foil or the like having a shape with a longitudinal direction and a lateral direction.
  • a long tape having a resin base material and an adhesive layer may be attached along the longitudinal direction to at least one main surface of the negative electrode.
  • the main surface means the surface facing the positive electrode.
  • the width of this tape is preferably 0.5 mm or more and 3 mm or less, for example. This tape has the role of preventing current collection failure due to tearing of the negative electrode when the lithium component of the negative electrode is consumed by a reaction at the end of discharge.
  • the material of the resin base material for example, fluorine resin, polyimide, polyphenylene sulfide, polyethersulfone, polyethylene, polyolefin such as polypropylene, polyethylene terephthalate, and the like can be used. Among them, polyolefin is preferred, and polypropylene is more preferred.
  • the adhesive layer contains, for example, at least one component selected from the group consisting of rubber components, silicone components and acrylic resin components.
  • synthetic rubber, natural rubber, or the like can be used as the rubber component.
  • Synthetic rubbers include butyl rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, neoprene, polyisobutylene, acrylonitrile-butadiene rubber, styrene-isoprene block copolymer, styrene-butadiene block copolymer, styrene-ethylene-butadiene block A copolymer etc. are mentioned.
  • silicone component an organic compound having a polysiloxane structure, a silicone-based polymer, or the like can be used.
  • silicone-based polymers include peroxide-curable silicones and addition-reactive silicones.
  • acrylic resin component polymers containing acrylic monomers such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters can be used.
  • Acrylic monomers such as ethyl, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate alone or in combination A polymer etc. are mentioned.
  • the adhesive layer may contain a cross-linking agent, a plasticizer, and a tackifier.
  • non-aqueous electrolyte for example, a non-aqueous electrolytic solution in which lithium salt or lithium ion is dissolved in a non-aqueous solvent can be used.
  • Non-aqueous solvent examples include organic solvents that can be generally used in non-aqueous electrolytes for lithium primary batteries.
  • Non-aqueous solvents include ethers, esters, carbonate esters and the like.
  • dimethyl ether, ⁇ -butyl lactone, propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane and the like can be used.
  • the non-aqueous electrolyte may contain one non-aqueous solvent, or may contain two or more non-aqueous solvents.
  • the non-aqueous solvent preferably contains a cyclic carbonate with a high boiling point and a chain ether with low viscosity even at low temperatures.
  • the cyclic carbonate preferably contains at least one selected from the group consisting of propylene carbonate (PC) and ethylene carbonate (EC), with PC being particularly preferred.
  • the chain ether preferably has a viscosity of 1 mPa ⁇ s or less at 25° C., and particularly preferably contains dimethoxyethane (DME).
  • the viscosity of the non-aqueous solvent can be obtained by measurement using a trace sample viscometer m-VROC manufactured by Leosence Corporation at a temperature of 25° C. and a shear rate of 10000 (1/s).
  • the form of the electrolyte is not limited to liquid, and may be gel or solid (polymer solid electrolyte).
  • the non-aqueous electrolyte may contain a lithium salt other than the cyclic imide component.
  • Lithium salts include, for example, lithium salts used as solutes in lithium primary batteries. Examples of such lithium salts include LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 , LiClO 4 , LiBF 4 , LiPF 6 , LiRaSO 3 (Ra is a fluorinated alkyl group having 1 to 4 carbon atoms), LiFSO 3 , LiN(SO 2 Rb)(SO 2 Rc) (Rb and Rc are each independently a fluorinated alkyl group having 1 to 4 carbon atoms), LiN(FSO 2 ) 2 , LiPO 2 F 2 , LiB(C 2 O 4 ) 2 and LiBF 2 (C 2 O 4 ).
  • the non-aqueous electrolyte may contain one kind of these lithium salts, or two or more kinds thereof.
  • the concentration of lithium ions contained in the electrolytic solution is, for example, 0.2 to 2.0 mol/L, and may be 0.3 to 1.5 mol/L.
  • the electrolyte may contain additives as necessary.
  • additives include propane sultone, vinylene carbonate, and the like.
  • the total concentration of such additives contained in the non-aqueous electrolyte is, for example, 0.003-5 mol/L.
  • Lithium primary batteries usually have a separator interposed between a positive electrode and a negative electrode.
  • a porous sheet made of an insulating material that is resistant to the internal environment of the lithium primary battery may be used.
  • synthetic resin nonwoven fabrics, synthetic resin microporous membranes, laminates thereof, and the like can be mentioned.
  • Synthetic resins used for nonwoven fabrics include polypropylene, polyphenylene sulfide, and polybutylene terephthalate.
  • Synthetic resins used for the microporous membrane include, for example, polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymers.
  • the microporous membrane may contain inorganic particles, if necessary.
  • the thickness of the separator is, for example, 5 ⁇ m or more and 100 ⁇ m or less.
  • the separator may be a single layer film made of one kind of material, or a composite film or multilayer film made of two or more kinds of materials.
  • gasket The material of the gasket is not particularly limited, and may be appropriately selected in consideration of the stability to the electrolyte, heat resistance, and the like. Specifically, polypropylene, polyethylene, polyphenylene sulfide, polyetherketone, polyamide, polyimide, liquid crystal polymer, copolymer of perfluoroalkoxyethylene, and the like may be used. These can be used alone or in combination of two or more, and can also be used in combination with fillers such as inorganic fibers.
  • the gasket may contain, for example, a rubber material.
  • the gasket may be composed of a single layer of a rubber material layer containing a rubber material, or may have a multi-layer structure of a rubber material layer and a fluororesin layer.
  • the rubber material butyl rubber (isobutylene-isoprene copolymer) (IIR) is preferable.
  • IIR isobutylene-isoprene copolymer
  • Butyl rubber has stable elasticity and stable sealing repulsion due to peroxide cross-linking or resin cross-linking.
  • Butyl rubber has lower gas permeability and higher insulating properties than other rubber materials, so it can maintain high performance of electrochemical devices even during long-term storage.
  • PTFE polytetratafluoroethane
  • PVDF polyvinylidene fluoride
  • PFA perfluoroalkoxyalkane
  • ETFE ethylene-tetrafluoroethylene copolymer
  • FEP perfluoroethylene-propene copolymers
  • Compression molding is performed on a single layer of butyl rubber only, or on multiple layers of fluororesin and butyl rubber.
  • a portion of the molded sheet may be punched to obtain individual pieces of the gasket, and at the same time, a tapered surface may be formed on a portion of the butyl rubber layer during the punching operation.
  • a configuration in which the fractured surface 13k of the butyl rubber layer is formed on a part of the tapered surface can provide a gasket with higher productivity.
  • Materials for the current collector include copper, aluminum, stainless steel, iron, nickel, palladium, gold, silver, and platinum. These may be used alone or as an alloy containing two or more.
  • the outer diameter of the current collecting rod can be appropriately set in consideration of the size of the battery, the strength of the current collecting rod, workability, etc.
  • the outer diameter of the collector rod may be, for example, 0.5 to 50 mm or 0.5 to 10 mm at the portion inserted into the through-hole of the gasket.
  • the outer diameter of the collector rod may be 1 to 6 mm or 1 to 4 mm at the portion inserted into the through-hole of the gasket. good.
  • cylindrical case Materials for the cylindrical case include silver, copper, iron, nickel, palladium, gold, platinum, aluminum, and stainless steel.
  • the thickness of the cylindrical case can be set as appropriate, but may be 50 to 500 ⁇ m, or 100 to 300 ⁇ m, in consideration of strength and workability.
  • FIG. 4 shows a front view with a partial cross section of a cylindrical lithium primary battery according to an embodiment of the present disclosure.
  • a lithium primary battery 10 includes a cylindrical case 11, a wound electrode group 12 housed in the case 11, and a gasket 13 for sealing the case 11.
  • the wound electrode group 12 includes a collector rod 14, a negative electrode 15, a positive electrode 16, and a separator 17 for separating the negative electrode 15 and the positive electrode 16.
  • the wound electrode group 12 includes a non-aqueous Electrolytes are in contact.
  • the collector rod 14 is electrically connected to the negative electrode 15 at the winding start position (innermost circumference) of the winding electrode group 12 .
  • One end of the collector rod 14 is inserted into the through hole 13 h of the gasket 13 .
  • the opening side end portion of the tubular case 11 is sealed by forming a diameter-reduced portion 35 , whereby the opening of the tubular case 11 is sealed by the gasket 13 .
  • One end of the collector rod 14 is exposed to the outside of the cylindrical case 11 , and is used as an external negative electrode terminal of the lithium primary battery 10 .
  • a positive electrode 16 is wound around the outermost periphery of the wound electrode group 12 .
  • a positive electrode current collector (not shown) is exposed at the outermost positive electrode 16 , and the positive electrode current collector is in contact with the inner peripheral surface of the cylindrical case 11 so as to apply pressure. . Thereby, the cylindrical case 11 and the positive electrode 16 are electrically connected.
  • An insulating cover 34 is provided on the outer surface of the cylindrical case 11 , and the portion where the insulating cover 34 is not provided is used as an external positive electrode terminal of the lithium primary battery 10 .
  • An insulating cap 33 is provided at the other end of the current collecting rod 14 so as not to cause a short circuit with the cylindrical case 11 .
  • the electrochemical device of the present disclosure maintains high sealing performance even in long-term use, it can be suitably used, for example, as a main power source or memory backup power source for various meters.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
PCT/JP2022/035255 2021-12-24 2022-09-21 電気化学デバイスおよびその製造方法 Ceased WO2023119765A1 (ja)

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JP2023569069A JP7664533B2 (ja) 2021-12-24 2022-09-21 電気化学デバイスおよびその製造方法

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6459760A (en) * 1987-08-28 1989-03-07 Matsushita Electric Industrial Co Ltd Slender organic electrolyte battery
JP2005085553A (ja) * 2003-09-05 2005-03-31 Sanyo Electric Co Ltd 非水電解質電池
CN202231090U (zh) * 2011-07-15 2012-05-23 山东圣阳电源股份有限公司 一种铅酸蓄电池端柱与电池盖的密封结构
JP2013048105A (ja) * 2008-07-03 2013-03-07 Samsung Sdi Co Ltd キャップ組立体、二次電池及び二次電池の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6459760A (en) * 1987-08-28 1989-03-07 Matsushita Electric Industrial Co Ltd Slender organic electrolyte battery
JP2005085553A (ja) * 2003-09-05 2005-03-31 Sanyo Electric Co Ltd 非水電解質電池
JP2013048105A (ja) * 2008-07-03 2013-03-07 Samsung Sdi Co Ltd キャップ組立体、二次電池及び二次電池の製造方法
CN202231090U (zh) * 2011-07-15 2012-05-23 山东圣阳电源股份有限公司 一种铅酸蓄电池端柱与电池盖的密封结构

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