WO2013024774A1 - Cylindrical secondary battery - Google Patents

Cylindrical secondary battery Download PDF

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Publication number
WO2013024774A1
WO2013024774A1 PCT/JP2012/070248 JP2012070248W WO2013024774A1 WO 2013024774 A1 WO2013024774 A1 WO 2013024774A1 JP 2012070248 W JP2012070248 W JP 2012070248W WO 2013024774 A1 WO2013024774 A1 WO 2013024774A1
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WO
WIPO (PCT)
Prior art keywords
negative electrode
metal
secondary battery
cylindrical
battery
Prior art date
Application number
PCT/JP2012/070248
Other languages
French (fr)
Japanese (ja)
Inventor
右一 江幡
勇人 小口
磯野　栄一
Original Assignee
日立ビークルエナジー株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日立ビークルエナジー株式会社 filed Critical 日立ビークルエナジー株式会社
Priority to JP2013528985A priority Critical patent/JP5747082B2/en
Publication of WO2013024774A1 publication Critical patent/WO2013024774A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/538—Connection of several leads or tabs of wound or folded electrode stacks
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/533—Electrode connections inside a battery casing characterised by the shape of the leads or tabs
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0422—Cells or battery with cylindrical casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0431—Cells with wound or folded electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a cylindrical secondary battery, and more particularly to a cylindrical secondary battery in which a current collecting member connected to one of positive and negative electrodes and a battery can are joined by welding or the like.
  • a cylindrical secondary battery typified by a lithium secondary battery or the like contains an electrode group in which a positive electrode and a negative electrode are wound around a shaft core via a separator in a cylindrical battery can, An electrolyte is injected and configured.
  • the positive and negative electrodes have positive and negative active materials coated on both sides of the positive and negative metal foils, respectively.
  • Each of the positive and negative metal foils has a number of positive and negative electrode tabs (hereinafter referred to as “electrode tabs”) arranged at a predetermined pitch along one side edge in the longitudinal direction.
  • the positive and negative electrode tabs are respectively wound around the outer periphery of a substantially ring-shaped positive and negative current collecting member, and are joined to each current collecting member by ultrasonic welding or the like with the electrode tabs superimposed. .
  • One of the positive and negative current collecting members is joined to a battery lid disposed on the top of the battery can, and the other is joined to the bottom of the battery can by, for example, resistance welding.
  • the battery can is made of iron and the current collecting member is made of copper
  • the connecting force formed by nickel is usually interposed between the battery can and the current collecting member because the joining force by welding is insufficient. By doing so, a sufficient bonding force is obtained.
  • an opening through which the shaft core is inserted is provided in the center of the current collecting member, and connection leads extending on both sides of the opening are closed on the bottom surface side of the current collecting member.
  • a cylindrical secondary battery to be joined is known. In such a cylindrical secondary battery, a portion corresponding to the opening of the axial center of the connection lead is pressed and welded to the bottom of the battery can with an electrode rod for resistance welding (see, for example, Patent Document 1). .
  • a cylindrical secondary battery has an electrode group in which a positive electrode and a negative electrode are wound with a separator interposed around a cylindrical shaft core and an opening on the upper side.
  • the battery can in which the electrode group is accommodated and the electrolyte is injected, the battery lid disposed on the upper side of the battery can, and the bottom of the battery can and the lower end of the shaft core,
  • the negative electrode current collecting member has a ring shape having an outer peripheral side wall on the outer peripheral side, and the negative electrode current collecting member has the shaft in the central portion.
  • a cylindrical recess into which the tip end side of the battery is inserted is formed.
  • the second metal is joined to the bottom of the battery can. It is joined to the metal by ultrasonic welding.
  • the second metal is diffusion-fused over the entire surface on the one surface side of the first metal.
  • the second metal preferably has a thickness of 0.2 to 0.7 mm.
  • the cylindrical recess of the current collecting member is formed with a plurality of protrusions that contact the outer periphery of the shaft core.
  • a gap that is spaced from the outer periphery of the shaft core is formed between the protrusions of the cylindrical recess, and the cylindrical recess. It is preferable that an opening penetrating from the inside to the outside of the cylindrical recess is formed between the protruding portions.
  • the second metal is formed in a partial region including the center of the concave cylindrical portion on one surface side of the first metal. can do.
  • the second metal has a width smaller than the width of the concave cylindrical portion and from one end side of the outer peripheral side wall of the negative electrode current collecting member. It can be formed linearly on the other end side.
  • the second metal includes the center of the ring-shaped negative electrode current collecting member up to the end of the outer peripheral side wall in plan view.
  • the protrusion protruding toward the bottom of the battery can is formed on the bottom surface of the cylindrical recess.
  • the metal 2 is preferably formed on the surface of the protrusion facing the bottom of the can.
  • the current collecting member is formed of a clad material in which the first metal and the second metal diffused and fused to the first metal are integrated.
  • the contact area between the first metal and the second metal can be increased. Therefore, the contact resistance value of the joint portion of the first and second metals can be reduced. Thereby, the thickness of the expensive second metal can be reduced, and the cost can be reduced.
  • FIG. 1 is a cross-sectional view of an embodiment of a cylindrical secondary battery according to the present invention.
  • FIG. 2 is an exploded perspective view of the cylindrical secondary battery shown in FIG. 1.
  • FIG. 2 is an enlarged cross-sectional view of a periphery of a negative electrode current collecting member illustrated in FIG. 1.
  • A) is sectional drawing of the negative electrode current collection member illustrated in FIG. 3
  • B) is the bottom view. Sectional drawing for demonstrating the method of welding a negative electrode current collection member to the can bottom of a battery can.
  • FIG. 8 is a characteristic diagram showing the rate of change in resistance value with respect to the thickness of a nickel material, which is a first-order differentiation of FIG. 7.
  • (A) is sectional drawing of the negative electrode current collection member illustrated by FIG. 9,
  • (B) is the bottom view.
  • (A) is sectional drawing of the negative electrode current collection member illustrated in FIG. 11, (B) is the bottom view.
  • (A) is sectional drawing of the negative electrode current collection member illustrated by FIG. 13, (B) is the bottom view.
  • Embodiment 5 of the cylindrical secondary battery of this invention is shown, (A) is an expanded sectional view of a negative electrode current collection member peripheral part, (B) is a top view and sectional drawing of the material of a negative electrode current collection member .
  • the negative electrode current collection member illustrated by FIG. 15 is shown, (A) is sectional drawing, (B) is a bottom view.
  • FIG. 1 is an enlarged cross-sectional view showing an embodiment of a cylindrical secondary battery of the present invention.
  • the cylindrical secondary battery 1 is, for example, a lithium ion secondary battery.
  • the cylindrical secondary battery 1 includes a cylindrical battery can 2 and a battery container 3 formed of a hat-type battery lid 3 that seals the upper portion of the battery can 2. It is accommodated and infused with a non-aqueous electrolyte 5.
  • the cylindrical battery can 2 is made of, for example, iron (SPCC), and nickel plating is applied to both the inner and outer surfaces.
  • SPCC iron
  • a groove 2 a protruding to the inside of the battery can 2 is formed on the opening 2 b provided on the upper end side.
  • An electrode group 10 is disposed inside the battery can 2.
  • the electrode group 10 includes a cylindrical shaft core 15 having a hollow portion along the axial direction, and a positive electrode and a negative electrode wound around the shaft core 15 via a separator.
  • FIG. 2 is an exploded perspective view of the cylindrical secondary battery 1 shown in FIG.
  • the electrode group 10 has a structure in which a positive electrode 11, a negative electrode 12, and a separator 13 are wound around an axis 15.
  • the outermost periphery of the electrode group 10 is wound so as to be the negative electrode 12 and the separator 13 on the outer periphery thereof.
  • a side edge of the outermost separator 13 is fixed to the inner separator 13 by an adhesive tape 19.
  • the positive electrode 11 includes a positive electrode metal foil that is formed of an aluminum foil and has a long shape, and a positive electrode mixture treatment portion 11a in which a positive electrode mixture is applied to both surfaces of the positive electrode metal foil.
  • the upper side edge extending in the longitudinal direction of the positive electrode metal foil is a positive electrode mixture untreated portion where the positive electrode mixture is not applied and the aluminum foil is exposed.
  • a number of positive electrode tabs 16 protruding in parallel with the axial direction of the shaft core 15 are integrally formed at equal intervals in the positive electrode mixture untreated portion.
  • the positive electrode mixture is composed of a positive electrode active material, a positive electrode conductive material, and a positive electrode binder.
  • the positive electrode active material is preferably lithium oxide. Examples include lithium cobaltate, lithium manganate, lithium nickelate, lithium composite oxide (lithium oxide containing two or more selected from cobalt, nickel, and manganese).
  • the positive electrode binder can bind the positive electrode active material and the positive electrode conductive material, and can bind the positive electrode mixture and the positive electrode current collector, and must be significantly deteriorated by contact with the non-aqueous electrolyte 5.
  • the positive electrode binder include polyvinylidene fluoride (PVDF) and fluororubber.
  • PVDF polyvinylidene fluoride
  • fluororubber An example of the coating thickness of the positive electrode mixture is about 40 ⁇ m on one side.
  • the negative electrode 12 includes a negative electrode metal foil that is formed of a copper foil and has a long shape, and a negative electrode mixture treatment portion 12a in which a negative electrode mixture is applied to both surfaces of the negative electrode metal foil.
  • the lower side edge extending in the longitudinal direction of the negative electrode metal foil is a negative electrode mixture untreated portion where the negative electrode mixture is not applied and the copper foil is exposed.
  • a large number of negative electrode tabs 17 extending in parallel to the axial direction of the shaft core 15 and in the direction opposite to the positive electrode tab 16 are integrally formed at equal intervals. Yes.
  • the negative electrode mixture includes a negative electrode active material, a negative electrode binder, and a thickener.
  • the negative electrode mixture may have a negative electrode conductive material such as acetylene black.
  • As the negative electrode active material it is preferable to use graphitic carbon, particularly artificial graphite.
  • An example of the coating thickness of the negative electrode mixture is about 40 ⁇ m on one side.
  • the separator 13 is formed of, for example, a porous film made of a composite material of polypropylene (PP) and polyethylene (PE) having a thickness of 40 ⁇ m.
  • PP polypropylene
  • PE polyethylene
  • a substantially ring-shaped positive electrode current collecting member 31 is press-fitted on the inner peripheral side of the upper end portion of the hollow cylindrical shaft core 15.
  • the positive electrode current collecting member 31 is made of, for example, aluminum. All of the positive electrode tabs 16 of the positive electrode 11 are joined to the ring-shaped peripheral side surface of the positive electrode current collecting member 31 by ultrasonic welding or the like. When the positive electrode tab 16 is ultrasonically welded to the positive electrode current collecting member 31, the positive electrode tab 16 is disposed on the ring-shaped peripheral side surface of the positive electrode current collecting member 31, and the ribbon 41 is wound around the positive electrode tab 16. Weld from above.
  • a substantially ring-shaped negative electrode current collecting member 20 is press-fitted and attached to the lower end portion of the shaft core 15.
  • the negative electrode current collecting member 20 is made of, for example, copper.
  • the negative electrode tabs 17 of the negative electrode 12 are all joined to the ring-shaped peripheral side surface of the negative electrode current collecting member 20 by ultrasonic welding or the like. When the negative electrode tab 17 is ultrasonically welded to the negative electrode current collector member 20, the negative electrode tab 17 is disposed on the ring-shaped peripheral side surface of the negative electrode current collector member 20, and the ribbon 42 is wound around the negative electrode tab 17. Weld from above.
  • the lower surface of the negative electrode current collecting member 20 is joined to the can bottom 2 c of the battery can 2. Details of the structure of the negative electrode current collecting member 20 and the method of joining the battery can 2 to the can bottom 2c will be described later.
  • a flexible positive electrode conductive lead 32 formed by laminating a plurality of aluminum foils is joined to the upper surface of the positive electrode current collecting member 31 by ultrasonic welding or the like.
  • the positive electrode conductive lead 32 can flow a large current by laminating and integrating a plurality of aluminum foils, and is provided with flexibility.
  • a conductive connection plate 33 is disposed on the upper part of the positive electrode current collecting member 31.
  • the battery lid 3 is fixed to the peripheral edge of the conductive connection plate 33 by caulking.
  • the conductive connection plate 33 is made of aluminum or an aluminum alloy and has a substantially disk shape.
  • a substantially circular safety valve is formed in the substantially central portion of the conductive connection plate 33 to release a gas generated in the cylindrical secondary battery 1 in the case of overcharge or the like.
  • the safety valve is formed by a portion that is crushed so as to form a substantially V-shaped groove by pressing and is formed into a thin portion.
  • the other end of the positive electrode conductive lead 32 having one end bonded to the positive electrode current collecting member 31 is bonded to the lower surface of the conductive connection plate 33 by laser welding or the like.
  • a gasket 34 is provided to cover the peripheral edge of the conductive connection plate 33.
  • the gasket 34 is made of, for example, a pull fluoroalkoxy fluororesin (PFA).
  • PFA pull fluoroalkoxy fluororesin
  • the battery lid 3 caulked to the peripheral edge of the conductive connecting plate 33 is fixed to the battery can 2 together with the gasket 34 by caulking.
  • the conductive connecting plate 33 with the battery lid 3 crimped therein is accommodated in the opening of the gasket 34 and the gasket 34 is crimped together with the peripheral edge of the opening 2b of the battery can 2 by pressing, as shown in FIG. Then, a battery container in which the battery cover 3, the conductive connection plate 33, the gasket 34, and the battery cover 3 are integrated by caulking is produced.
  • a predetermined amount of non-aqueous electrolyte 5 is injected into the battery can 2.
  • the nonaqueous electrolytic solution 5 it is preferable to use a solution in which a lithium salt is dissolved in a carbonate solvent.
  • the lithium salt include lithium fluorophosphate (LiPF 6 ), lithium fluoroborate (LiBF 6 ), and the like.
  • carbonate solvents include ethylene carbonate (EC), dimethyl carbonate (DMC), propylene carbonate (PC), methyl ethyl carbonate (MEC), or a mixture of solvents selected from one or more of the above solvents. Can be mentioned.
  • a plurality of openings 15 a are formed to allow the nonaqueous electrolyte solution to flow out from the hollow portion of the shaft core 15 to the outside of the shaft core 15 when the nonaqueous electrolyte solution 5 is injected.
  • the electrode group 10 in which the negative electrode current collecting member 20 is press-fitted into the lower end portion of the shaft core 15 and the positive electrode current collecting member 31 is press-fitted into the upper end portion of the shaft core 15 is accommodated in the battery can 2, and the negative electrode current collecting member 20 is The battery can 2 is joined to the bottom 2 c of the battery can 2, and the non-aqueous electrolyte 5 is injected into the battery can 2.
  • the positive electrode current collecting member 31 and the conductive connecting plate 33 on which the battery lid 3 is caulked are connected by the positive electrode conductive lead 32.
  • the cylindrical secondary battery 1 shown in FIG. 1 is manufactured by caulking the conductive connection plate 33 and the battery lid 3 to the peripheral edge of the opening 2b on the upper side of the battery can 2 via the gasket 34. Is done.
  • FIG. 3 is an enlarged cross-sectional view of the negative electrode current collecting member 20 and the periphery of the can bottom 2c of the battery can 2 shown in FIG. 4A is a cross-sectional view of the negative electrode current collecting member 20 shown in FIG. 3, and FIG. 4B is a bottom view thereof.
  • the negative electrode current collecting member 20 has a ring-shaped peripheral wall on the outer peripheral side and the inner peripheral side, and is formed in a substantially cylindrical shape as a whole. That is, a cylindrical recess 29 having a ring-shaped inner peripheral side wall 20a is formed at the center, and a structure having a ring-shaped outer peripheral side wall 20b on the outer peripheral side.
  • a substantially disk-shaped intermediate flat portion 20c is formed between the inner peripheral side wall 20a and the outer peripheral side wall 20b.
  • the inner peripheral side wall 20a is formed to rise substantially vertically from the bottom 29a of the cylindrical recess 29 toward the intermediate flat part 20c
  • the outer peripheral side wall 20b is formed to fall substantially vertically on the outer peripheral edge of the intermediate flat part 20c.
  • a projection 20d that protrudes toward the can bottom 2c is formed at the center of the cylindrical recess 29 of the negative electrode current collecting member 20.
  • the negative electrode current collecting member 20 includes the first metal layer 21 having the inner peripheral side wall 20a, the outer peripheral side wall 20b, and the intermediate flat portion 20c, and the second metal diffused and fused to the first metal layer 21.
  • the metal layer 22 is formed of an integrated clad material.
  • the second metal layer 22 is formed on one surface of the first metal layer 21 over the entire surface of the first metal layer 21.
  • the first metal layer 21 is formed of, for example, copper or a copper alloy copper-based metal
  • the second metal layer is formed of, for example, nickel. Nickel has a resistance value larger than that of copper, but the bonding force by resistance welding with iron which is a material of the battery can 2 is larger than that of copper.
  • the second metal layer 22 is disposed on the inner surface side of the can bottom 2c of the battery can 2, and resistance welding is performed on the can bottom 2c of the battery can 2.
  • the second metal layer 22 is formed on the outer surface side of the bottom 29 a of the cylindrical recess 29 of the first metal layer 21, and the lower end portion of the shaft core 15 is placed in the cylindrical recess 29 of the negative electrode current collector 20. In the inserted state, the second metal layer 22 faces the inner surface of the can bottom 2 c of the battery can 2.
  • the inner peripheral side wall 20a is formed with a plurality of protruding portions 25 protruding toward the inner surface side in the radial direction of the cylindrical recess 29.
  • a circular space is formed by the tip of the protruding portion 25, and the outer peripheral surface of the shaft core 15 is fitted into the circular space by press-fitting. Accordingly, a gap 26 is formed between the adjacent projecting portions 25 of the inner peripheral side wall 20 a and the shaft core 15.
  • the shaft core 15 fitted in the cylindrical recess 29 is shown by a two-dot chain line.
  • the fitting portion becomes a bag shape and the fluidity of the non-aqueous electrolyte 5 is interrupted. Is done.
  • the fluidity of the non-aqueous electrolyte 5 can be ensured by providing a plurality of protrusions 25 on the inner peripheral side wall 20a and forming the gaps 26 between the protrusions 25. it can.
  • openings 27 are formed so as to penetrate from the inner side to the outer side of the cylindrical concave portion 29 of the negative electrode current collecting member 20 corresponding to each gap portion 26.
  • eight circular openings 28 are formed in the intermediate flat portion 20 c of the negative electrode current collecting member 20.
  • the openings 27 and 28 are for ensuring the fluidity of the non-aqueous electrolyte 5 and for degassing the gas generated inside the battery when overcharged.
  • the gas generated in the non-aqueous electrolyte 5 and the battery can flow on the inner side of the shaft core 15 and on the electrode group 10 side without flowing on the negative electrode tab 17 side. Is considered.
  • the opening 27 formed in the inner peripheral side wall 20a of the negative electrode current collecting member 20 is exemplified as a structure formed corresponding to each gap portion 26, the present invention is not limited to this, and the gap portions 26 are not limited thereto.
  • a plurality of openings 27 may be formed, or portions where the openings 27 are not formed at a predetermined interval may be provided.
  • the total thickness of the negative electrode current collecting member 20 is about 1.0 mm.
  • the thickness of the nickel material that is the second metal layer 22 is recommended to be about 0.2 to 0.7 mm.
  • FIG. 6 is a characteristic diagram showing the relationship between the thickness of the nickel material and the bonding force of the battery can 2.
  • the joining force required for joining the bottom 2 c of the battery can 2 and the negative electrode current collecting member 20 is set to 1.
  • the thickness of the nickel material was 0.1 mm, the required joining force could not be obtained, and the average was about 25% insufficient.
  • the thickness of the nickel material was 0.3 mm, a joining force exceeding the required joining force was obtained, and the average value was about 150%. From the above experimental results, if the thickness of the nickel material is 0.2 mm, it becomes 110% or more of the required bonding force, and a sufficient bonding force can be obtained.
  • FIG. 7 is a characteristic diagram showing the resistance value with respect to the thickness of the nickel material.
  • the resistance value characteristic up to a thickness of 1 mm is shown with the resistance value being 1 when the thickness of the nickel material is 0.2 mm.
  • FIG. 8 is a first-order differentiation of FIG. 7, and is a characteristic diagram showing the rate of change in resistance value with respect to the thickness of the nickel material.
  • the nickel material has a changing point in the vicinity of 0.7 mm. That is, when the thickness of the nickel material exceeds about 0.7 mm, the resistance value increases rapidly. This means that the internal resistance of the battery suddenly rises and the battery output is greatly reduced. From the above, it is recommended that the thickness of the nickel material be about 0.2 to 0.7 mm.
  • the electrode group 10 is produced.
  • the positive electrode mixture processing part 11a is formed on both surfaces of the positive electrode metal foil, and the positive electrode 11 in which a number of positive electrode tabs 16 are formed along one side edge in the longitudinal direction of the positive electrode metal foil is produced.
  • the negative electrode mixture processing part 12a is formed in both surfaces of negative electrode metal foil, and the negative electrode 12 in which many negative electrode tabs 17 were formed along the other side edge of the longitudinal direction of negative electrode metal foil is produced.
  • the separator 13, the positive electrode 11, the separator 13, and the negative electrode 12 are wound around the shaft core 15 to produce the electrode group 10.
  • the positive electrode tab 16 of the positive electrode 11 and the negative electrode tab 17 of the negative electrode 12 are laminated so as to be located on opposite sides.
  • the separator 13 on the outermost periphery of the electrode group 10 is bonded with an adhesive tape 19.
  • the negative electrode current collecting member 20 is produced.
  • the negative electrode current collecting member 20 made of the clad material in which the first metal layer 21 and the second metal layer 22 diffused and fused to the first metal layer 21 are integrated is manufactured.
  • the clad material is obtained by hot-rolling the first metal thin plate formed on the first metal layer 21 and the second metal thin plate formed on the second metal layer 22 to obtain the first and second metals.
  • the thin plate is fabricated by metal diffusion bonding at the joining region.
  • the clad material is pressed to form the negative electrode current collecting member 20 shown in FIGS. 4A and 4B having the inner peripheral side wall 20a, the outer peripheral side wall 20b, the intermediate flat portion 20c, and the protrusion 20d. .
  • the lower end portion of the shaft core 15 is press-fitted into the cylindrical recess 29 of the negative electrode current collecting member 20, and the lower end surface of the shaft core 15 is brought into contact with the bottom surface of the cylindrical recess 29.
  • the position of the negative electrode current collecting member 20 in the vertical direction in other words, the axial direction is determined.
  • the negative electrode tab 17 is almost uniformly distributed and adhered to the outer peripheral surface of the outer peripheral side wall 20b of the negative electrode current collecting member 20, and the negative electrode tab 17 is joined to the negative electrode current collecting member 20 by ultrasonic welding.
  • the ribbon 42 is wound around the negative electrode tab 17 and welded from above the ribbon 42.
  • the lower portion of the positive electrode current collecting member 31 is press-fitted inside the upper end portion of the shaft core 15.
  • the positive electrode tab 16 of the positive electrode 11 is closely_contact
  • the ribbon 41 is wound around the positive electrode tab 16 and welded from above the ribbon 41.
  • one end of the positive electrode conductive lead 32 is joined to one surface of the positive electrode current collecting member 31 by ultrasonic welding or the like.
  • the positive electrode conductive lead 32 is removed from the position corresponding to the hollow portion of the shaft core 15 so as not to obstruct the injection of the non-aqueous electrolyte 5. In this way, the power generation unit is configured.
  • a cylindrical battery can 2 that can accommodate the power generation unit is formed by drawing or the like. Then, the power generation unit manufactured as described above is accommodated in the battery can 2.
  • the can bottom 2c of the battery can 2 corresponding to the periphery of the protrusion 20d of the negative electrode current collecting member 20 accommodated in the battery can 2 is supported by a welding jig 91.
  • the electrode rod 92 is inserted into the hollow portion of the shaft core 15.
  • a cross-sectional view of this state is shown in FIG.
  • the lower end surface of the electrode bar 92 is pressed against the upper surface of the bottom 29 a of the cylindrical recess 29 of the negative electrode current collector member 20, that is, the upper surface of the first metal layer 21.
  • the second metal layer 22 of the negative electrode current collecting member 20 comes into contact with the inner surface of the can bottom 2 c of the battery can 2.
  • the electrode rod 92 and the welding jig 91 are energized, and the negative electrode current collecting member 20 is joined to the can bottom 2c of the battery can 2 by resistance welding or the like.
  • the protrusion 20d of the negative electrode current collecting member 20 is melted and flattened. Accordingly, the entire bottom portion 29 a of the cylindrical recess 29 of the negative electrode current collecting member 20, that is, the bottom portion of the second metal layer 22 is joined to the can bottom 2 c of the battery can 2.
  • the second metal layer 22 is formed over the entire surface of the first metal layer 21 and has a large contact area. For this reason, the contact resistance between the first metal layer 21 and the second metal layer 22 can be reduced.
  • the negative electrode current collecting member 20 is formed with a cylindrical concave portion 29 corresponding to the hollow portion of the shaft core 15, and the cylindrical concave portion 29 includes the first metal layer 21, the second metal layer 22, and the like. Are laminated and formed by metal diffusion bonding. Therefore, the resistance value can be greatly reduced as compared with the conventional structure in which the connection can made of the nickel material alone is joined to the bottom of the battery can 2.
  • a part on the upper end side of the battery can 2 protrudes inward of the diaphragm by grooving, and a substantially U-shaped groove 2a is formed on the outer surface.
  • injection of electrolyte a predetermined amount of the non-aqueous electrolyte 5 is injected into the battery can 2.
  • the non-aqueous electrolyte 5 is injected from the upper part of the hollow portion of the shaft core 15. As described above, the non-aqueous electrolyte 5 injected from the upper part of the hollow part of the shaft core 15 flows from the upper part toward the lower part of the shaft core 15, and the opening 15 a of the shaft core 15.
  • the negative electrode current collecting member 20 flows out from the inner side of the shaft core 15 through the path of the gap 26 and the opening 27.
  • the positive electrode conductive lead 32 is folded back as shown by a dotted line in FIG.
  • the battery cover 3 is caulked and integrated with the periphery of the conductive connection plate 33.
  • a gasket 34 is accommodated in the upper part of the groove 2 a of the battery can 2.
  • a conductive connection plate 33 to which the battery cover 3 is fixed is disposed above the gasket 34.
  • the conductive connection plate 33 is inclined, and the other end of the positive electrode conductive lead 32 whose one end is welded to the positive electrode current collecting member 31 is joined to the conductive connection plate 33 by laser welding or the like.
  • FIG. 10 (Embodiment 2) 9 is a cross-sectional view showing Embodiment 2 of the cylindrical secondary battery of the present invention
  • FIG. 10 (A) is a cross-sectional view of the negative electrode current collector shown in FIG. 9, and FIG. ) Is a bottom view thereof.
  • the negative electrode current collecting member 20A does not have a ring-shaped outer peripheral side wall 20b (see FIG. 4A). That is, the negative electrode current collecting member 20A has a ring-shaped inner peripheral side wall 20a that rises substantially perpendicularly from the bottom 29a of the cylindrical recess 29, and a flat disk-shaped part 20c1 that is bent substantially perpendicularly from the inner peripheral side wall 20a. It is formed into a shape.
  • the configuration in which the negative electrode current collecting member 20A is formed of a clad material in which a first metal layer 21 and a second metal layer 22 diffused and fused to the first metal layer are integrated is an embodiment. Same as 1.
  • the negative electrode current collecting member 20A in Embodiment 2 has a structure in which the second metal layer 22 is formed on the entire lower surface of the flat disk-shaped portion 20c1. For this reason, the negative electrode tab 17 of the negative electrode 12 is joined to the second metal layer 22 at the peripheral edge of the disc-like portion 20c1 of the negative electrode current collecting member 20A.
  • the copper-based metal that is the material of the negative electrode tab 17 and the nickel that is the material of the second metal layer 22 of the negative electrode current collector 20A are difficult to join by ultrasonic welding. For this reason, in Embodiment 2, joining by the negative electrode tab 17 and the 2nd metal layer 22 of 20 A of negative electrode current collection members is recommended by laser welding.
  • the area can be reduced by eliminating the outer peripheral side wall 20b, and the weight can be reduced and the cost can be reduced.
  • Other configurations in the second embodiment are the same as those in the first embodiment, and the corresponding members are denoted by the same reference numerals and description thereof is omitted.
  • FIG. 11 is a cross-sectional view showing Embodiment 3 of the cylindrical secondary battery of the present invention
  • FIG. 12 (A) is a cross-sectional view of the negative electrode current collecting member shown in FIG. ) Is a bottom view thereof.
  • the third embodiment is different from the first embodiment in that the second metal layer 22 is formed only in a partial region of the first metal layer 21 in the negative electrode current collecting member 20B. That is, as illustrated in FIGS. 12A and 12B, in the negative electrode current collector 20 ⁇ / b> B according to the third embodiment, the second metal layer 22 has a width smaller than the diameter of the bottom 29 a of the cylindrical recess 29. Thus, it is formed on one surface side of the first metal layer 21 in a straight line passing through the center of the negative electrode current collecting member 20B.
  • this negative electrode current collecting member 20B In order to produce this negative electrode current collecting member 20B, the second metal thin plate formed on the second metal layer 22 is fitted in advance to the first metal thin plate formed on the first metal layer 21. A groove is formed. Then, the first metal thin plate and the second metal thin plate are hot-rolled in a state where the second metal thin plate is fitted in the groove of the first metal thin plate, and the first and second metal thin plates are joined. A clad material is produced by metal diffusion bonding in the region. Thereafter, similarly to the first embodiment, the negative electrode current collecting member 20B is formed by pressing the clad material.
  • the cost can be reduced.
  • Other configurations in the third embodiment are the same as those in the first embodiment, and the corresponding members are denoted by the same reference numerals and description thereof is omitted.
  • FIG. 14 (Embodiment 4) 13 is a cross-sectional view showing Embodiment 4 of the cylindrical secondary battery of the present invention
  • FIG. 14 (A) is a cross-sectional view of the negative electrode current collector shown in FIG. 13, and FIG. ) Is a bottom view thereof.
  • the negative electrode current collecting member 20C does not have a ring-shaped outer peripheral side wall 20b (see FIG. 12A). That is, the negative electrode current collecting member 20C includes a ring-shaped inner peripheral side wall 20a that rises substantially vertically from the bottom 29a of the cylindrical recess 29, and a flat disk-shaped portion 20c2 that is bent substantially vertically from the inner peripheral side wall 20a. It is formed in the shape to have.
  • the negative electrode current collecting member 20C in Embodiment 4 has a structure in which the second metal layer 22 is formed on a part of the lower surface of the flat disk-shaped portion 20c2. That is, the flat disk-shaped part 20c2 is formed of only the first metal layer 21 except for a part thereof. For this reason, the negative electrode tab 17 of the negative electrode 12 is disposed close to the region where the first metal layer 21 is exposed, avoiding the portion where the second metal layer 22 is formed, and thus the negative electrode tab 17 and the negative electrode current collecting member 20C can be joined by ultrasonic welding.
  • the outer peripheral side wall 20 b is not provided as compared with the first embodiment, and the second metal layer 22 is formed only on a part of the first metal layer 21. Therefore, the area of the second metal layer 22 can be made smaller than those in the second and third embodiments.
  • Other configurations in the fourth embodiment are the same as those in the first embodiment, and the corresponding members are denoted by the same reference numerals and description thereof is omitted.
  • FIGS. 15 and 16 are views for explaining Embodiment 5 of the cylindrical secondary battery of the present invention
  • FIG. 15A is a cross-sectional view of the periphery of the negative electrode current collecting member of the cylindrical secondary battery
  • 16A is a cross-sectional view of the negative electrode current collector shown in FIG. 15A
  • FIG. 16B is a bottom view thereof.
  • the second metal layer 22 is formed in a partial region of the first metal layer 21 in the negative electrode current collecting member 20 ⁇ / b> D.
  • the fifth embodiment is different from the third embodiment in that the second metal layer 22 is formed not only in the central region of the negative electrode current collecting member 20D but also in a region more than half of the negative electrode current collecting member 20D including the central region. It is a point that has been. That is, as illustrated in FIGS. 16A and 16B, in the negative electrode current collector 20D according to Embodiment 5, the second metal layer 22 is the center of the cylindrical recess 29 in the negative electrode current collector 20D. A boundary portion with the first metal layer 21 is provided at a position where the first metal layer 21 has been cut in by a predetermined width.
  • the second metal layer 22 extends over the entire region from this boundary portion to the end of the outer peripheral side wall 20b of the negative electrode current collecting member 20D, including the region of the protrusion 20d formed in the center of the cylindrical recess 29. It is formed on one surface of one metal layer 21.
  • FIG. 15B is a plan view and a cross-sectional view of a material for the negative electrode current collecting member 20D.
  • a thin portion for fitting the second metal thin plate formed on the second metal layer 22 is formed on the first metal thin plate formed on the first metal layer 21 in advance. Keep it. Then, the first metal thin plate and the second metal thin plate are hot-rolled in a state where the second metal thin plate is fitted to the thin portion of the first metal thin plate, and the first and second metal thin plates are A clad material is produced by metal diffusion bonding in the junction region. Thereafter, similarly to the third embodiment, the negative electrode current collecting member 20D is formed by pressing the clad material.
  • the negative electrode current collector members 20 and 20A to 20C are connected to the first metal layer 21 to which one of the positive and negative electrode tabs 16 and 17 is connected,
  • the clad material was formed by diffusion fusion with the metal layer 21 and the second metal layer 22 joined to the can bottom 2 c of the battery can 2. For this reason, the contact area of the 1st metal layer 21 and the 2nd metal layer 22 becomes a whole surface contact, and the contact resistance of the 1st, 2nd metal layers 21 and 22 can be reduced. Since the contact resistance of the first and second metals is reduced, the thickness of the expensive second metal can be reduced, and the cost can be reduced.
  • the area of the expensive second metal layer 22 can be made smaller by eliminating the outer peripheral side wall 20b and making it flat.
  • the area of the expensive second metal layer 22 can be made smaller.
  • the second metal layer 22 is formed in a circular shape in plan view from the center of the negative electrode current collector 20D to the end of the outer peripheral side 20b of the negative electrode current collector 20D. If the layer 22 is formed in more than half of the region 22, the material cost can be reduced and the productivity can be improved.
  • a plurality of protrusions 25 that come into contact with the outer periphery of the shaft core 15 are provided in the cylindrical recesses 29 of the negative electrode current collecting members 20 and 20A to 20C to which the shaft core 15 is fitted. Since 26 is formed, the fluidity of the non-aqueous electrolyte 5 can be ensured.
  • the opening 27 is provided at a position corresponding to each gap portion 26 of the inner peripheral side wall 20a of the negative electrode current collecting member 20, 20A to 20C, the fluidity of the non-aqueous electrolyte 5 is ensured, and overcharge or the like is performed. Degassing of the generated gas can be improved.
  • the plate thickness is set to about 0.2 mm to 0.7 mm, so that the joining force with the battery can 2 is satisfied and the resistance value is A small characteristic part is efficiently utilized, and the cylindrical secondary battery 1 having good characteristics can be formed.
  • the first metal layer 21 is made of copper or a copper alloy
  • the second metal layer 22 is made of nickel.
  • the first metal layer 21 and the second metal layer 22 are not limited to this.
  • the second metal layer 22 is made of stainless steel.
  • the second metal layer 22 is made of aluminum or an aluminum alloy. can do.
  • the metal material constituting the second metal layer 22 a material having a larger bonding force with the battery can 2 than the first metal layer 21 may be used.
  • the present invention can also be applied to a cylindrical secondary battery using a water-soluble electrolyte such as a nickel metal hydride battery, a nickel cadmium battery, or a lead storage battery.
  • a water-soluble electrolyte such as a nickel metal hydride battery, a nickel cadmium battery, or a lead storage battery.
  • the case where the negative electrode current collecting member 20 is joined to the battery can 2 is the negative electrode.
  • the present invention can also be applied to the case where the battery can side that joins the positive electrode current collecting member 31 to the battery can 2 is the positive electrode because the connection structure between the battery can and the current collecting member is the same.
  • the cylindrical secondary battery of the present invention can be applied with various modifications within the scope of the invention.
  • the negative electrode current collecting members 20, 20A to 20C are connected to the positive and negative electrodes.

Abstract

A collector member is formed from a cladding material in which a first metal is integrated with a second metal, wherein a positive electrode or a negative electrode is connected to the first metal, and the second metal is diffused and fused to the first metal and is joined to the bottom of a battery case.

Description

円筒形二次電池Cylindrical secondary battery
　この発明は、円筒形二次電池に関し、より詳細には、正・負極電極の一方に接続された集電部材と電池缶とが溶接等により接合された円筒形二次電池に関する。 The present invention relates to a cylindrical secondary battery, and more particularly to a cylindrical secondary battery in which a current collecting member connected to one of positive and negative electrodes and a battery can are joined by welding or the like.
　リチウム二次電池等に代表される円筒形二次電池は、円筒形の電池缶内に、正極電極と負極電極とがセパレータを介して軸芯の周囲に捲回された電極群が収容され、電解液が注入されて構成される。正・負極の電極は、それぞれ、正・負極の金属箔の両面に塗工された、正・負極の活物質を有する。正・負極の金属箔は、それぞれ、長手方向の片側縁に沿って所定のピッチで配列された多数の正・負極タブ（以下、「電極タブ」という）を有する。 A cylindrical secondary battery typified by a lithium secondary battery or the like contains an electrode group in which a positive electrode and a negative electrode are wound around a shaft core via a separator in a cylindrical battery can, An electrolyte is injected and configured. The positive and negative electrodes have positive and negative active materials coated on both sides of the positive and negative metal foils, respectively. Each of the positive and negative metal foils has a number of positive and negative electrode tabs (hereinafter referred to as “electrode tabs”) arranged at a predetermined pitch along one side edge in the longitudinal direction.
　正・負極の電極タブは、それぞれ、ほぼリング形状の正・負極の集電部材の外周に捲回され、電極タブが重ね合わされた状態で、各集電部材に超音波溶接等により接合される。
　正・負極の集電部材の一方は、電池缶の上部に配置された電池蓋に接合され、他方は電池缶の缶底に、例えば、抵抗溶接により接合される。
　電池缶が鉄により形成され、集電部材が銅により形成されている場合、溶接による接合力が不足するため、通常、電池缶と集電部材との間にニッケルにより形成された接続リードを介在させることにより、十分な接合力が得られるようにしている。 The positive and negative electrode tabs are respectively wound around the outer periphery of a substantially ring-shaped positive and negative current collecting member, and are joined to each current collecting member by ultrasonic welding or the like with the electrode tabs superimposed. .
One of the positive and negative current collecting members is joined to a battery lid disposed on the top of the battery can, and the other is joined to the bottom of the battery can by, for example, resistance welding.
When the battery can is made of iron and the current collecting member is made of copper, the connecting force formed by nickel is usually interposed between the battery can and the current collecting member because the joining force by welding is insufficient. By doing so, a sufficient bonding force is obtained.
　このような構造として、集電部材の中央に、軸芯が挿通される開口部を設け、集電部材の底面側に、この開口部を塞いで開口部の両側に延出された接続リードを接合する円筒形二次電池が知られている。このような円筒形二次電池では、接続リードの軸芯の開口部に対応する部分を、抵抗溶接用の電極棒により電池缶の缶底に圧接して溶接する（例えば、特許文献１参照）。 As such a structure, an opening through which the shaft core is inserted is provided in the center of the current collecting member, and connection leads extending on both sides of the opening are closed on the bottom surface side of the current collecting member. A cylindrical secondary battery to be joined is known. In such a cylindrical secondary battery, a portion corresponding to the opening of the axial center of the connection lead is pressed and welded to the bottom of the battery can with an electrode rod for resistance welding (see, for example, Patent Document 1). .
日本国特開２００９－２８９７１４号公報Japanese Unexamined Patent Publication No. 2009-289714
　特許文献１に記載された発明では、集電部材の中央に開口部が形成され、この開口部を塞いで延出された接続リードの両端部が集電部材の周縁部に接合される。この場合、特許文献１には、明確に記載されていないが、通常、接続リードと集電部材とは、スポット溶接により接合される。従って、接続リードと集電部材との接合面積はかなり小さくなっている。このため、接続リードと集電部材との接合部の抵抗値が大きくなり、電池内部の抵抗値が増大する。抵抗値を小さくするためには、接続リードの厚さを厚くする必要があるが、ニッケル等で構成される接続リードは、銅等により構成される集電部材よりも高価である。したがって、接続部材の厚さが厚い分だけコスト高となっていた。 In the invention described in Patent Document 1, an opening is formed in the center of the current collecting member, and both end portions of the connection lead extended by closing the opening are joined to the peripheral portion of the current collecting member. In this case, although not clearly described in Patent Document 1, the connection lead and the current collecting member are usually joined by spot welding. Therefore, the bonding area between the connection lead and the current collecting member is considerably reduced. For this reason, the resistance value of the joint portion between the connection lead and the current collecting member increases, and the resistance value inside the battery increases. In order to reduce the resistance value, it is necessary to increase the thickness of the connection lead. However, the connection lead made of nickel or the like is more expensive than the current collecting member made of copper or the like. Therefore, the cost is increased by the thickness of the connecting member.
　本発明の第１の態様によると、円筒形二次電池は、円筒状の軸芯の周囲に、正極電極と負極電極とをセパレータを介して捲回した電極群と上部側に開口部を有し、電極群が収容されると共に電解液が注入された電池缶と、電池缶の上部側に配置された電池蓋と、電池缶の缶底と軸芯の下端部との間に配置され、負極タブが接続されると共に電池缶に接合された負極集電部材とを備え、負極集電部材は、負極電極の一方の電タブが接続される第１の金属と、第１の金属に拡散融合され、電池缶の缶底に接合された第２の金属とが一体化したクラッド材により形成され、第１の金属は、銅または銅合金で形成され、第２の金属はニッケルで形成され、負極集電部材は、外周側に外周側壁を有するリング状であり、負極集電部材は、中央部に前記軸芯の先端部側が挿入される筒状凹部が形成され、筒状凹部において、第２の金属は前記電池缶の缶底に接合され、負極集電部材の外周側壁において、前記負極タブは前記第１の金属に超音波溶接により接合されている。
　本発明の第２の態様によると、第１の態様の円筒形二次電池において、第２の金属は、第１の金属の一面側の全面に拡散融合されていることが好ましい。
　本発明の第３の態様によると、第１または２の態様の円筒形二次電池において、第２の金属は、０．２～０．７ｍｍの厚さを有することが好ましい。　本発明の第４の態様によると、第１の態様の円筒形二次電池において、集電部材の筒状凹部には、軸芯の外周に接触する複数の突出部が形成されていることが好ましい。
　本発明の第５の態様によると、第４の態様の円筒形二次電池において、筒状凹部の突出部間には、軸芯の外周から離間する空隙部が形成されると共に、筒状凹部の突出部間には、筒状凹部の内側から外側に貫通する開口が形成されていることが好ましい。
　本発明の第６の態様によると、第１の態様の円筒形二次電池において、第２の金属は、第１の金属の一面側において、凹状筒部の中心を含む一部の領域に形成することができる。
　本発明の第７の態様によると、第６の態様の円筒形二次電池において、第２の金属は、凹状筒部の幅よりも小さい幅で、負極集電部材の外周側壁の一端側から他端側に直線状に形成することができる。
　本発明の第８の態様によると、第６の態様の円筒形二次電池において、第２の金属は、リング状の負極集電部材の中心を含んで、外周側壁の端部まで、平面視で前記負極集電部材の半分以上の領域に形成することができる。
　本発明の第９の態様によると、第１乃至８のいずれか１つの態様の円筒形二次電池において、筒状凹部の底面に電池缶の缶底側に向かって突き出す突起が形成され、第２の金属は、突起の缶底側に対面する表面に形成されていることが望ましい。 According to the first aspect of the present invention, a cylindrical secondary battery has an electrode group in which a positive electrode and a negative electrode are wound with a separator interposed around a cylindrical shaft core and an opening on the upper side. The battery can in which the electrode group is accommodated and the electrolyte is injected, the battery lid disposed on the upper side of the battery can, and the bottom of the battery can and the lower end of the shaft core, A negative electrode current collector member connected to the battery can and connected to the negative electrode tab; the negative electrode current collector member diffuses into the first metal to which one of the negative electrode tabs is connected; Fused and formed by a clad material integrated with a second metal joined to the bottom of the battery can, the first metal is formed of copper or a copper alloy, and the second metal is formed of nickel. The negative electrode current collecting member has a ring shape having an outer peripheral side wall on the outer peripheral side, and the negative electrode current collecting member has the shaft in the central portion. A cylindrical recess into which the tip end side of the battery is inserted is formed. In the cylindrical recess, the second metal is joined to the bottom of the battery can. It is joined to the metal by ultrasonic welding.
According to the second aspect of the present invention, in the cylindrical secondary battery according to the first aspect, it is preferable that the second metal is diffusion-fused over the entire surface on the one surface side of the first metal.
According to the third aspect of the present invention, in the cylindrical secondary battery according to the first or second aspect, the second metal preferably has a thickness of 0.2 to 0.7 mm. According to the fourth aspect of the present invention, in the cylindrical secondary battery according to the first aspect, the cylindrical recess of the current collecting member is formed with a plurality of protrusions that contact the outer periphery of the shaft core. preferable.
According to the fifth aspect of the present invention, in the cylindrical secondary battery according to the fourth aspect, a gap that is spaced from the outer periphery of the shaft core is formed between the protrusions of the cylindrical recess, and the cylindrical recess. It is preferable that an opening penetrating from the inside to the outside of the cylindrical recess is formed between the protruding portions.
According to the sixth aspect of the present invention, in the cylindrical secondary battery according to the first aspect, the second metal is formed in a partial region including the center of the concave cylindrical portion on one surface side of the first metal. can do.
According to the seventh aspect of the present invention, in the cylindrical secondary battery of the sixth aspect, the second metal has a width smaller than the width of the concave cylindrical portion and from one end side of the outer peripheral side wall of the negative electrode current collecting member. It can be formed linearly on the other end side.
According to the eighth aspect of the present invention, in the cylindrical secondary battery according to the sixth aspect, the second metal includes the center of the ring-shaped negative electrode current collecting member up to the end of the outer peripheral side wall in plan view. And can be formed in a region of more than half of the negative electrode current collector.
According to the ninth aspect of the present invention, in the cylindrical secondary battery according to any one of the first to eighth aspects, the protrusion protruding toward the bottom of the battery can is formed on the bottom surface of the cylindrical recess. The metal 2 is preferably formed on the surface of the protrusion facing the bottom of the can.
　この発明の円筒形二次電池によれば、集電部材は、第１の金属と、第１の金属に拡散融合された第２の金属とが一体化したクラッド材により形成されており、第１の金属と第２の金属との接触面積を大きくすることができる。従って、第１、第２の金属の接合部の接抵抗値を低減することができる。これにより、高価な第２の金属の厚さを薄くすることができ、コストを低減することができる。 According to the cylindrical secondary battery of the present invention, the current collecting member is formed of a clad material in which the first metal and the second metal diffused and fused to the first metal are integrated. The contact area between the first metal and the second metal can be increased. Therefore, the contact resistance value of the joint portion of the first and second metals can be reduced. Thereby, the thickness of the expensive second metal can be reduced, and the cost can be reduced.
本発明に係る円筒形二次電池の一実施の形態の断面図。1 is a cross-sectional view of an embodiment of a cylindrical secondary battery according to the present invention. 図１に示された円筒形二次電池の分解斜視図。FIG. 2 is an exploded perspective view of the cylindrical secondary battery shown in FIG. 1. 図１に図示された負極集電部材周辺部の拡大断面図。FIG. 2 is an enlarged cross-sectional view of a periphery of a negative electrode current collecting member illustrated in FIG. 1. （Ａ）は、図３に図示された負極集電部材の断面図であり、（Ｂ）は、その底面図。(A) is sectional drawing of the negative electrode current collection member illustrated in FIG. 3, (B) is the bottom view. 負極集電部材を電池缶の缶底に溶接する方法を説明するための断面図。Sectional drawing for demonstrating the method of welding a negative electrode current collection member to the can bottom of a battery can. ニッケル材の板厚と電池缶の接合力との関係を示す特性図。The characteristic view which shows the relationship between the board | plate thickness of nickel material, and the joining force of a battery can. ニッケル材の厚さに対する抵抗値を示す特性図。The characteristic view which shows the resistance value with respect to the thickness of nickel material. 図７を１次微分した図であり、ニッケル材の厚さに対する抵抗値の変化率を示す特性図。FIG. 8 is a characteristic diagram showing the rate of change in resistance value with respect to the thickness of a nickel material, which is a first-order differentiation of FIG. 7. 本発明の円筒形二次電池の実施形態２の要部の断面図。Sectional drawing of the principal part of Embodiment 2 of the cylindrical secondary battery of this invention. （Ａ）は、図９に図示された負極集電部材の断面図であり、（Ｂ）は、その底面図。(A) is sectional drawing of the negative electrode current collection member illustrated by FIG. 9, (B) is the bottom view. 本発明の円筒形二次電池の実施形態３の要部の断面図。Sectional drawing of the principal part of Embodiment 3 of the cylindrical secondary battery of this invention. （Ａ）は、図１１に図示された負極集電部材の断面図であり、（Ｂ）は、その底面図。(A) is sectional drawing of the negative electrode current collection member illustrated in FIG. 11, (B) is the bottom view. 本発明の円筒形二次電池の実施形態４の要部の断面図。Sectional drawing of the principal part of Embodiment 4 of the cylindrical secondary battery of this invention. （Ａ）は、図１３に図示された負極集電部材の断面図であり、（Ｂ）は、その底面図。(A) is sectional drawing of the negative electrode current collection member illustrated by FIG. 13, (B) is the bottom view. 本発明の円筒形二次電池の実施形態５を示し、（Ａ）は、負極集電部材周辺部の拡大断面図であり、（Ｂ）は、負極集電部材の材料の平面図と断面図。 Embodiment 5 of the cylindrical secondary battery of this invention is shown, (A) is an expanded sectional view of a negative electrode current collection member peripheral part, (B) is a top view and sectional drawing of the material of a negative electrode current collection member . 図１５に図示された負極集電部材を示し、（Ａ）は断面図、（Ｂ）は底面図。The negative electrode current collection member illustrated by FIG. 15 is shown, (A) is sectional drawing, (B) is a bottom view.
　（実施形態１）
--円筒形二次電池の構造--
　以下、この発明の円筒形二次電池の一実施の形態を図面と共に説明する。
　図１は、この発明の円筒形二次電池の一実施の形態を示す拡大断面図である。
　円筒形二次電池１は、例えば、リチウムイオン二次電池である。この円筒形二次電池１は、円筒形の電池缶２および電池缶２の上部を封口するハット型の電池蓋３で構成される電池容器内に、以下に説明する発電用の各構成部材が収容され、非水電解液５が注入されて構成されている。 (Embodiment 1)
--Structure of cylindrical secondary battery--
Hereinafter, an embodiment of a cylindrical secondary battery of the present invention will be described with reference to the drawings.
FIG. 1 is an enlarged cross-sectional view showing an embodiment of a cylindrical secondary battery of the present invention.
The cylindrical secondary battery 1 is, for example, a lithium ion secondary battery. The cylindrical secondary battery 1 includes a cylindrical battery can 2 and a battery container 3 formed of a hat-type battery lid 3 that seals the upper portion of the battery can 2. It is accommodated and infused with a non-aqueous electrolyte 5.
　円筒形の電池缶２は、例えば、鉄（ＳＰＣＣ）製であり、内外両面にはニッケルめっきが施されている。電池缶２には、上端側に設けられた開口部２ｂ側に電池缶２の内側に突き出した溝２ａが形成されている。
　電池缶２の内部には、電極群１０が配置されている。電極群１０は、軸方向に沿う中空部を有する円筒形の軸芯１５と、軸芯１５の周囲にセパレータを介して捲回された正極電極および負極電極とを備えている。 The cylindrical battery can 2 is made of, for example, iron (SPCC), and nickel plating is applied to both the inner and outer surfaces. In the battery can 2, a groove 2 a protruding to the inside of the battery can 2 is formed on the opening 2 b provided on the upper end side.
An electrode group 10 is disposed inside the battery can 2. The electrode group 10 includes a cylindrical shaft core 15 having a hollow portion along the axial direction, and a positive electrode and a negative electrode wound around the shaft core 15 via a separator.
　図２は、図１に示された円筒形二次電池１の分解斜視図である。
　図２に図示されるように、電極群１０は、軸芯１５の周囲に、正極電極１１、負極電極１２、およびセパレータ１３が捲回された構造を有する。電極群１０の最外周が、負極電極１２およびその外周のセパレータ１３となるように捲回されている。最外周のセパレータ１３の側縁は接着テープ１９により、内周側のセパレータ１３に止められる。 FIG. 2 is an exploded perspective view of the cylindrical secondary battery 1 shown in FIG.
As shown in FIG. 2, the electrode group 10 has a structure in which a positive electrode 11, a negative electrode 12, and a separator 13 are wound around an axis 15. The outermost periphery of the electrode group 10 is wound so as to be the negative electrode 12 and the separator 13 on the outer periphery thereof. A side edge of the outermost separator 13 is fixed to the inner separator 13 by an adhesive tape 19.
　正極電極１１は、アルミニウム箔により形成され長尺な形状を有する正極金属箔と、この正極金属箔の両面に正極合剤が塗布された正極合剤処理部１１ａを有する。正極金属箔の長手方向に延在する上方側の側縁は、正極合剤が塗布されずアルミニウム箔が露出した正極合剤未処理部となっている。この正極合剤未処理部には、軸芯１５の軸方向と平行に突き出す多数の正極タブ１６が等間隔に一体的に形成されている。 The positive electrode 11 includes a positive electrode metal foil that is formed of an aluminum foil and has a long shape, and a positive electrode mixture treatment portion 11a in which a positive electrode mixture is applied to both surfaces of the positive electrode metal foil. The upper side edge extending in the longitudinal direction of the positive electrode metal foil is a positive electrode mixture untreated portion where the positive electrode mixture is not applied and the aluminum foil is exposed. A number of positive electrode tabs 16 protruding in parallel with the axial direction of the shaft core 15 are integrally formed at equal intervals in the positive electrode mixture untreated portion.
　正極合剤は正極活物質と、正極導電材と、正極バインダとからなる。正極活物質はリチウム酸化物が好ましい。例として、コバルト酸リチウム、マンガン酸リチウム、ニッケル酸リチウム、リチウム複合酸化物（コバルト、ニッケル、マンガンから選ばれる２種類以上を含むリチウム酸化物）等が挙げられる。 The positive electrode mixture is composed of a positive electrode active material, a positive electrode conductive material, and a positive electrode binder. The positive electrode active material is preferably lithium oxide. Examples include lithium cobaltate, lithium manganate, lithium nickelate, lithium composite oxide (lithium oxide containing two or more selected from cobalt, nickel, and manganese).
　正極バインダは、正極活物質と正極導電材を結着させ、また正極合剤と正極集電体を結着させることが可能であり、非水電解液５との接触により、大幅に劣化しなければ特に制限はない。正極バインダの例としてポリフッ化ビニリデン（ＰＶＤＦ）やフッ素ゴムなどが挙げられる。
　正極合剤の塗布厚さの一例としては片側約４０μｍである。 The positive electrode binder can bind the positive electrode active material and the positive electrode conductive material, and can bind the positive electrode mixture and the positive electrode current collector, and must be significantly deteriorated by contact with the non-aqueous electrolyte 5. There are no particular restrictions. Examples of the positive electrode binder include polyvinylidene fluoride (PVDF) and fluororubber.
An example of the coating thickness of the positive electrode mixture is about 40 μm on one side.
　負極電極１２は、銅箔により形成され長尺な形状を有する負極金属箔と、この負極金属箔の両面に負極合剤が塗布された負極合剤処理部１２ａを有する。負極金属箔の長手方向に延在する下方側の側縁は、負極合剤が塗布されず銅箔が露出した負極合剤未処理部となっている。この負極合剤未処理部には、軸芯１５の軸方向と平行に、かつ、正極タブ１６とは反対方向に延出された、多数の負極タブ１７が等間隔に一体的に形成されている。 The negative electrode 12 includes a negative electrode metal foil that is formed of a copper foil and has a long shape, and a negative electrode mixture treatment portion 12a in which a negative electrode mixture is applied to both surfaces of the negative electrode metal foil. The lower side edge extending in the longitudinal direction of the negative electrode metal foil is a negative electrode mixture untreated portion where the negative electrode mixture is not applied and the copper foil is exposed. In this negative electrode mixture untreated portion, a large number of negative electrode tabs 17 extending in parallel to the axial direction of the shaft core 15 and in the direction opposite to the positive electrode tab 16 are integrally formed at equal intervals. Yes.
　負極合剤は、負極活物質と、負極バインダと、増粘剤とからなる。負極合剤は、アセチレンブラックなどの負極導電材を有しても良い。負極活物質としては、黒鉛炭素を用いること、特に人造黒鉛を使用することが好ましい。
　負極合剤の塗布厚さの一例としては片側約４０μｍである。 The negative electrode mixture includes a negative electrode active material, a negative electrode binder, and a thickener. The negative electrode mixture may have a negative electrode conductive material such as acetylene black. As the negative electrode active material, it is preferable to use graphitic carbon, particularly artificial graphite.
An example of the coating thickness of the negative electrode mixture is about 40 μm on one side.
　セパレータ１３は、例えば、厚さ４０μｍのポリプロピレン（ＰＰ）とポリエチレン（ＰＥ）の複合材料からなる多孔膜で形成されている。 The separator 13 is formed of, for example, a porous film made of a composite material of polypropylene (PP) and polyethylene (PE) having a thickness of 40 μm.
　中空な円筒形状の軸芯１５の上端部の内周側に、ほぼリング状の正極集電部材３１が圧入されている。正極集電部材３１は、例えば、アルミニウムにより形成されている。
　正極電極１１の正極タブ１６は、すべて、正極集電部材３１のリング状の周側面に超音波溶接等により接合されている。正極タブ１６を正極集電部材３１に超音波溶接する場合、正極集電部材３１のリング状の周側面に正極タブ１６を配置し、この正極タブ１６上にリボン４１を巻き付けた状態でリボン４１上から溶接する。 A substantially ring-shaped positive electrode current collecting member 31 is press-fitted on the inner peripheral side of the upper end portion of the hollow cylindrical shaft core 15. The positive electrode current collecting member 31 is made of, for example, aluminum.
All of the positive electrode tabs 16 of the positive electrode 11 are joined to the ring-shaped peripheral side surface of the positive electrode current collecting member 31 by ultrasonic welding or the like. When the positive electrode tab 16 is ultrasonically welded to the positive electrode current collecting member 31, the positive electrode tab 16 is disposed on the ring-shaped peripheral side surface of the positive electrode current collecting member 31, and the ribbon 41 is wound around the positive electrode tab 16. Weld from above.
　軸芯１５の下端部には、ほぼリング形状の負極集電部材２０が圧入されて取り付けられている。負極集電部材２０は、例えば、銅により形成されている。
　負極電極１２の負極タブ１７は、すべて、負極集電部材２０のリング状の周側面に超音波溶接等により接合されている。負極タブ１７を負極集電部材２０に超音波溶接する場合、負極集電部材２０のリング状の周側面に負極タブ１７を配置し、この負極タブ１７上にリボン４２を巻き付けた状態でリボン４２上から溶接する。 A substantially ring-shaped negative electrode current collecting member 20 is press-fitted and attached to the lower end portion of the shaft core 15. The negative electrode current collecting member 20 is made of, for example, copper.
The negative electrode tabs 17 of the negative electrode 12 are all joined to the ring-shaped peripheral side surface of the negative electrode current collecting member 20 by ultrasonic welding or the like. When the negative electrode tab 17 is ultrasonically welded to the negative electrode current collector member 20, the negative electrode tab 17 is disposed on the ring-shaped peripheral side surface of the negative electrode current collector member 20, and the ribbon 42 is wound around the negative electrode tab 17. Weld from above.
　負極集電部材２０は、その下面が電池缶２の缶底２ｃに接合されている。負極集電部材２０の構造および電池缶２の缶底２ｃとの接合方法については、その詳細を後述する。 The lower surface of the negative electrode current collecting member 20 is joined to the can bottom 2 c of the battery can 2. Details of the structure of the negative electrode current collecting member 20 and the method of joining the battery can 2 to the can bottom 2c will be described later.
　正極集電部材３１の上面には、複数のアルミニウム箔が積層されて構成されたフレキシブルな正極導電リード３２が、その一端部を超音波溶接等により接合されている。正極導電リード３２は、複数枚のアルミニウム箔を積層して一体化することにより、大電流を流すことが可能とされ、且つ、フレキシブル性を付与されている。 A flexible positive electrode conductive lead 32 formed by laminating a plurality of aluminum foils is joined to the upper surface of the positive electrode current collecting member 31 by ultrasonic welding or the like. The positive electrode conductive lead 32 can flow a large current by laminating and integrating a plurality of aluminum foils, and is provided with flexibility.
　正極集電部材３１の上部には、導電接続板３３が配置されている。導電接続板３３の周縁部には電池蓋３が、かしめにより固定されている。
　導電接続板３３は、アルミニウムまたはアルミニウム合金により形成され、ほぼ円盤形状を有している。図示はしないが、導電接続板３３のほぼ中央部には、過充電等の場合に、円筒形二次電池１内部に発生するガスを放出するほぼ円形形状の安全弁が形成されている。安全弁は、プレスによりほぼＶ字形状の溝ができるように押し潰して薄肉部とされた部分で形成される。導電接続板３３の下面には、一端部が正極集電部材３１に接合された正極導電リード３２の他端部がレーザ溶接等により接合されている。 A conductive connection plate 33 is disposed on the upper part of the positive electrode current collecting member 31. The battery lid 3 is fixed to the peripheral edge of the conductive connection plate 33 by caulking.
The conductive connection plate 33 is made of aluminum or an aluminum alloy and has a substantially disk shape. Although not shown in the drawings, a substantially circular safety valve is formed in the substantially central portion of the conductive connection plate 33 to release a gas generated in the cylindrical secondary battery 1 in the case of overcharge or the like. The safety valve is formed by a portion that is crushed so as to form a substantially V-shaped groove by pressing and is formed into a thin portion. The other end of the positive electrode conductive lead 32 having one end bonded to the positive electrode current collecting member 31 is bonded to the lower surface of the conductive connection plate 33 by laser welding or the like.
　導電接続板３３の周縁部を覆ってガスケット３４が設けられている。ガスケット３４は、例えば、プルフルオロアルコキシフッ素樹脂（ＰＦＡ）等により形成されている。
　導電接続板３３の周縁部にかしめられた電池蓋３は、ガスケット３４と共に電池缶２にかしめにより固定されている。
　ガスケット３４の開口部内に、電池蓋３がかしめられた導電接続板３３を収容し、プレスにより、電池缶２の開口部２ｂの周縁部と共にガスケット３４を圧着すると、図１に図示されたような、電池蓋３、導電接続板３３、ガスケット３４、電池蓋３がかしめにより一体化された電池容器が作製される。 A gasket 34 is provided to cover the peripheral edge of the conductive connection plate 33. The gasket 34 is made of, for example, a pull fluoroalkoxy fluororesin (PFA).
The battery lid 3 caulked to the peripheral edge of the conductive connecting plate 33 is fixed to the battery can 2 together with the gasket 34 by caulking.
When the conductive connecting plate 33 with the battery lid 3 crimped therein is accommodated in the opening of the gasket 34 and the gasket 34 is crimped together with the peripheral edge of the opening 2b of the battery can 2 by pressing, as shown in FIG. Then, a battery container in which the battery cover 3, the conductive connection plate 33, the gasket 34, and the battery cover 3 are integrated by caulking is produced.
　電池缶２の内部には、非水電解液５が所定量注入されている。非水電解液５の一例としては、リチウム塩がカーボネート系溶媒に溶解した溶液を用いることが好ましい。リチウム塩の例として、フッ化リン酸リチウム（ＬｉＰＦ６）、フッ化ホウ酸リチウム（ＬｉＢＦ６）等が挙げられる。また、カーボネート系溶媒の例として、エチレンカーボネート（ＥＣ）、ジメチルカーボネート（ＤＭＣ）、プロピレンカーボネート（ＰＣ）、メチルエチルカーボネート（ＭＥＣ）、或いは上記溶媒の１種類以上から選ばれる溶媒を混合したものが挙げられる。 A predetermined amount of non-aqueous electrolyte 5 is injected into the battery can 2. As an example of the nonaqueous electrolytic solution 5, it is preferable to use a solution in which a lithium salt is dissolved in a carbonate solvent. Examples of the lithium salt include lithium fluorophosphate (LiPF 6 ), lithium fluoroborate (LiBF 6 ), and the like. Examples of carbonate solvents include ethylene carbonate (EC), dimethyl carbonate (DMC), propylene carbonate (PC), methyl ethyl carbonate (MEC), or a mixture of solvents selected from one or more of the above solvents. Can be mentioned.
　軸芯１５の下端部には、非水電解液５を注入した際に、非水電解液を軸芯１５の中空部から軸芯１５の外側に流出するための複数の開口部１５ａが形成されている。
　軸芯１５の下端部に負極集電部材２０が圧入され、軸芯１５の上端部に正極集電部材３１が圧入された電極群１０を電池缶２内に収容し、負極集電部材２０を電池缶２の缶底２ｃに接合し、非水電解液５を電池缶２内に注入する。
　次に、正極導電リード３２により正極集電部材３１と電池蓋３がかしめられた導電接続板３３を接続する。そして、ガスケット３４を介して導電接続板３３と電池蓋３とを電池缶２の上部側の開口部２ｂの周縁部にかしめることにより、図１に図示される円筒形二次電池１が作製される。 At the lower end portion of the shaft core 15, a plurality of openings 15 a are formed to allow the nonaqueous electrolyte solution to flow out from the hollow portion of the shaft core 15 to the outside of the shaft core 15 when the nonaqueous electrolyte solution 5 is injected. ing.
The electrode group 10 in which the negative electrode current collecting member 20 is press-fitted into the lower end portion of the shaft core 15 and the positive electrode current collecting member 31 is press-fitted into the upper end portion of the shaft core 15 is accommodated in the battery can 2, and the negative electrode current collecting member 20 is The battery can 2 is joined to the bottom 2 c of the battery can 2, and the non-aqueous electrolyte 5 is injected into the battery can 2.
Next, the positive electrode current collecting member 31 and the conductive connecting plate 33 on which the battery lid 3 is caulked are connected by the positive electrode conductive lead 32. Then, the cylindrical secondary battery 1 shown in FIG. 1 is manufactured by caulking the conductive connection plate 33 and the battery lid 3 to the peripheral edge of the opening 2b on the upper side of the battery can 2 via the gasket 34. Is done.
　図３は、図１に図示された負極集電部材２０と電池缶２の缶底２ｃ周辺部の拡大断面図である。また、図４（Ａ）は、図３に図示された負極集電部材２０の断面図であり、図４（Ｂ）は、その底面図である。
　負極集電部材２０は、外周側と内周側にリング状の周壁を有する、全体としてほぼ筒型形状に形成されている。つまり、中央部に、リング状の内周側壁２０ａを有する筒状凹部２９が形成され、外周側に、リング状の外周側壁２０ｂを有する構造を有する。内周側壁２０ａと外周側壁２０ｂとの間には、ほぼ円盤形状の中間平坦部２０ｃが形成されている。内周側壁２０ａは筒状凹部２９の底部２９ａから中間平坦部２０ｃに向けてほぼ垂直に立ち上げて形成され、外周側壁２０ｂは、中間平坦部２０ｃの外周縁において、ほぼ垂直に立ち下げて形成されている。
　また、負極集電部材２０の筒状凹部２９の中央には、缶底２ｃ側に向かって突き出す突起２０ｄが形成されている。 FIG. 3 is an enlarged cross-sectional view of the negative electrode current collecting member 20 and the periphery of the can bottom 2c of the battery can 2 shown in FIG. 4A is a cross-sectional view of the negative electrode current collecting member 20 shown in FIG. 3, and FIG. 4B is a bottom view thereof.
The negative electrode current collecting member 20 has a ring-shaped peripheral wall on the outer peripheral side and the inner peripheral side, and is formed in a substantially cylindrical shape as a whole. That is, a cylindrical recess 29 having a ring-shaped inner peripheral side wall 20a is formed at the center, and a structure having a ring-shaped outer peripheral side wall 20b on the outer peripheral side. A substantially disk-shaped intermediate flat portion 20c is formed between the inner peripheral side wall 20a and the outer peripheral side wall 20b. The inner peripheral side wall 20a is formed to rise substantially vertically from the bottom 29a of the cylindrical recess 29 toward the intermediate flat part 20c, and the outer peripheral side wall 20b is formed to fall substantially vertically on the outer peripheral edge of the intermediate flat part 20c. Has been.
In addition, a projection 20d that protrudes toward the can bottom 2c is formed at the center of the cylindrical recess 29 of the negative electrode current collecting member 20.
　負極集電部材２０は、上記の如く、内周側壁２０ａ、外周側壁２０ｂおよび中間平坦部２０ｃを有する第１の金属層２１と、この第１の金属層２１に金属拡散融合された第２の金属層２２とが一体化されたクラッド材により形成されている。
　第２の金属層２２は、第１の金属層２１の一面に、第１の金属層２１の全面に亘り形成されている。
　第１の金属層２１は、例えば、銅または銅合金の銅系金属により形成されており、第２の金属層は、例えば、ニッケルにより形成されている。ニッケルは、抵抗値は銅よりも大きいが、電池缶２の材料である鉄との抵抗溶接による接合力は、銅の場合よりも大きい。 As described above, the negative electrode current collecting member 20 includes the first metal layer 21 having the inner peripheral side wall 20a, the outer peripheral side wall 20b, and the intermediate flat portion 20c, and the second metal diffused and fused to the first metal layer 21. The metal layer 22 is formed of an integrated clad material.
The second metal layer 22 is formed on one surface of the first metal layer 21 over the entire surface of the first metal layer 21.
The first metal layer 21 is formed of, for example, copper or a copper alloy copper-based metal, and the second metal layer is formed of, for example, nickel. Nickel has a resistance value larger than that of copper, but the bonding force by resistance welding with iron which is a material of the battery can 2 is larger than that of copper.
　そこで、電池缶２の缶底２ｃの内面側に第２の金属層２２を配置して、電池缶２の缶底２ｃに抵抗溶接する。
　第２の金属層２２は、第１の金属層２１の筒状凹部２９の底部２９ａの外面側に形成されており、負極集電部材２０の筒状凹部２９内に軸芯１５の下端部を挿入した状態で、第２の金属層２２が電池缶２の缶底２ｃの内面に対面する。 Therefore, the second metal layer 22 is disposed on the inner surface side of the can bottom 2c of the battery can 2, and resistance welding is performed on the can bottom 2c of the battery can 2.
The second metal layer 22 is formed on the outer surface side of the bottom 29 a of the cylindrical recess 29 of the first metal layer 21, and the lower end portion of the shaft core 15 is placed in the cylindrical recess 29 of the negative electrode current collector 20. In the inserted state, the second metal layer 22 faces the inner surface of the can bottom 2 c of the battery can 2.
　図４（Ｂ）に図示されるように、内周側壁２０ａには、筒状凹部２９の半径方向の内面側に突き出す複数の突出部２５が形成されている。突出部２５の先端部により円形の空間が形成され、この円形の空間に、軸芯１５の外周面が圧入により嵌合される。
　従って、内周側壁２０ａの隣接する突出部２５の間には、軸芯１５との間に空隙部２６が形成される。図４（Ｂ）において、筒状凹部２９内に嵌合された軸芯１５を二点鎖線により図示している。
　内周側壁２０ａの内面側に凹凸部が形成されていない構造では、筒状凹部２９に軸芯１５を嵌合すると、嵌合部分が袋状となって非水電解液５の流動性が遮断される。上記のように、内周側壁２０ａに複数の突出部２５を設け、各突出部２５間に空隙部２６が形成される構造とすることにより、非水電解液５の流動性を確保することができる。 As shown in FIG. 4B, the inner peripheral side wall 20a is formed with a plurality of protruding portions 25 protruding toward the inner surface side in the radial direction of the cylindrical recess 29. A circular space is formed by the tip of the protruding portion 25, and the outer peripheral surface of the shaft core 15 is fitted into the circular space by press-fitting.
Accordingly, a gap 26 is formed between the adjacent projecting portions 25 of the inner peripheral side wall 20 a and the shaft core 15. In FIG. 4B, the shaft core 15 fitted in the cylindrical recess 29 is shown by a two-dot chain line.
In the structure in which the concave and convex portion is not formed on the inner surface side of the inner peripheral side wall 20a, when the shaft core 15 is fitted into the cylindrical concave portion 29, the fitting portion becomes a bag shape and the fluidity of the non-aqueous electrolyte 5 is interrupted. Is done. As described above, the fluidity of the non-aqueous electrolyte 5 can be ensured by providing a plurality of protrusions 25 on the inner peripheral side wall 20a and forming the gaps 26 between the protrusions 25. it can.
　内周側壁２０ａには、各空隙部２６に対応して、負極集電部材２０の筒状凹部２９の内側から外側に貫通する開口２７が形成されている。また、負極集電部材２０の中間平坦部２０ｃには８個の円形の開口２８が形成されている。開口２７および２８は、非水電解液５の流動性の確保および過充電等の際に電池内部に発生するガスのガス抜きを図るためのものである。特に、開口２７を設けることにより、非水電解液５および電池内部に発生するガスは、負極タブ１７側を流動せずとも、軸芯１５の内側と電極群１０側を流動することができるように配慮されている。なお、負極集電部材２０の内周側壁２０ａに形成する開口２７は、各空隙部２６に対応して１つ形成された構造として例示されているが、これに限らず、各空隙部２６に対応して開口２７を複数個ずつ形成したり、あるいは、所定間隔で開口２７を形成しない部分を設けたりしてもよい。 In the inner peripheral side wall 20a, openings 27 are formed so as to penetrate from the inner side to the outer side of the cylindrical concave portion 29 of the negative electrode current collecting member 20 corresponding to each gap portion 26. In addition, eight circular openings 28 are formed in the intermediate flat portion 20 c of the negative electrode current collecting member 20. The openings 27 and 28 are for ensuring the fluidity of the non-aqueous electrolyte 5 and for degassing the gas generated inside the battery when overcharged. In particular, by providing the opening 27, the gas generated in the non-aqueous electrolyte 5 and the battery can flow on the inner side of the shaft core 15 and on the electrode group 10 side without flowing on the negative electrode tab 17 side. Is considered. In addition, although the opening 27 formed in the inner peripheral side wall 20a of the negative electrode current collecting member 20 is exemplified as a structure formed corresponding to each gap portion 26, the present invention is not limited to this, and the gap portions 26 are not limited thereto. Correspondingly, a plurality of openings 27 may be formed, or portions where the openings 27 are not formed at a predetermined interval may be provided.
　負極集電部材２０全体の厚さは、１．０ｍｍ程度である。第２の金属層２２であるニッケル材の厚さは、０．２～０．７ｍｍ程度とすることが推奨される。
　以下、分析データと共に、ニッケル材の厚さの変化に対する機械的および電気的特性について述べる。 The total thickness of the negative electrode current collecting member 20 is about 1.0 mm. The thickness of the nickel material that is the second metal layer 22 is recommended to be about 0.2 to 0.7 mm.
Hereinafter, mechanical and electrical characteristics with respect to changes in the thickness of the nickel material will be described together with the analysis data.
　図６は、ニッケル材の板厚と電池缶２の接合力との関係を示す特性図である。
　図６においては、電池缶２の缶底２ｃと負極集電部材２０との接合に必要とされる接合力を１としている。ニッケル材の板厚が０．１ｍｍの場合では、必要とされる接合力が得られず、平均で２５％程度不足していた。ニッケル材の板厚が０．３ｍｍの場合では、必要とされる接合力を超える接合力が得られ、その平均値は１５０％程度であった。
　上記実験結果より、ニッケル材の板厚が０．２ｍｍであれば、必要とされる接合力の１１０％以上となり、十分な接合力を得ることができる。 FIG. 6 is a characteristic diagram showing the relationship between the thickness of the nickel material and the bonding force of the battery can 2.
In FIG. 6, the joining force required for joining the bottom 2 c of the battery can 2 and the negative electrode current collecting member 20 is set to 1. When the thickness of the nickel material was 0.1 mm, the required joining force could not be obtained, and the average was about 25% insufficient. When the thickness of the nickel material was 0.3 mm, a joining force exceeding the required joining force was obtained, and the average value was about 150%.
From the above experimental results, if the thickness of the nickel material is 0.2 mm, it becomes 110% or more of the required bonding force, and a sufficient bonding force can be obtained.
　図７は、ニッケル材の厚さに対する抵抗値を示す特性図である。
　図７において、ニッケル材の厚さが０．２ｍｍの場合の抵抗値を１として、厚さ１ｍｍまでの抵抗値特性が図示されている。
　図８は、図７を１次微分した図であり、ニッケル材の厚さに対する抵抗値の変化率を示す特性図である。
　図８において、ニッケル材の厚さが０．７ｍｍ付近に変化点があることを明確に確認することができる。すなわち、ニッケル材の厚さが０．７ｍｍ程度を超えて厚くなると、抵抗値が急激に増大する。このことは、電池の内部抵抗が急に上昇して、電池出力の低下が大きいことを意味する。
　以上のことから、ニッケル材の厚さは、０．２～０．７ｍｍ程度とすることが推奨される。 FIG. 7 is a characteristic diagram showing the resistance value with respect to the thickness of the nickel material.
In FIG. 7, the resistance value characteristic up to a thickness of 1 mm is shown with the resistance value being 1 when the thickness of the nickel material is 0.2 mm.
FIG. 8 is a first-order differentiation of FIG. 7, and is a characteristic diagram showing the rate of change in resistance value with respect to the thickness of the nickel material.
In FIG. 8, it can be clearly confirmed that the nickel material has a changing point in the vicinity of 0.7 mm. That is, when the thickness of the nickel material exceeds about 0.7 mm, the resistance value increases rapidly. This means that the internal resistance of the battery suddenly rises and the battery output is greatly reduced.
From the above, it is recommended that the thickness of the nickel material be about 0.2 to 0.7 mm.
　次に、図１に図示された円筒形二次電池１の製造方法の一実施の形態を説明する。
--円筒形二次電池の製造方法--
〔電極群作製〕
　先ず、電極群１０を作製する。
　正極金属箔の両面に、正極合剤処理部１１ａが形成され、また、正極金属箔の長手方向の一側縁に沿って多数の正極タブ１６が形成された正極電極１１を作製する。また、負極金属箔の両面に負極合剤処理部１２ａが形成され、負極金属箔の長手方向の他側縁に沿って多数の負極タブ１７が形成された負極電極１２を作製する。
　そして、軸芯１５に、セパレータ１３、正極電極１１、セパレータ１３および負極電極１２を捲回して電極群１０を作製する。この場合、正極電極１１の正極タブ１６と負極電極１２の負極タブ１７とは、相対向する側に位置するように積層する。電極群１０の最外周のセパレータ１３を接着テープ１９により接着する。 Next, an embodiment of a method for manufacturing the cylindrical secondary battery 1 shown in FIG. 1 will be described.
--Method of manufacturing cylindrical secondary battery--
[Production of electrode group]
First, the electrode group 10 is produced.
The positive electrode mixture processing part 11a is formed on both surfaces of the positive electrode metal foil, and the positive electrode 11 in which a number of positive electrode tabs 16 are formed along one side edge in the longitudinal direction of the positive electrode metal foil is produced. Moreover, the negative electrode mixture processing part 12a is formed in both surfaces of negative electrode metal foil, and the negative electrode 12 in which many negative electrode tabs 17 were formed along the other side edge of the longitudinal direction of negative electrode metal foil is produced.
Then, the separator 13, the positive electrode 11, the separator 13, and the negative electrode 12 are wound around the shaft core 15 to produce the electrode group 10. In this case, the positive electrode tab 16 of the positive electrode 11 and the negative electrode tab 17 of the negative electrode 12 are laminated so as to be located on opposite sides. The separator 13 on the outermost periphery of the electrode group 10 is bonded with an adhesive tape 19.
［負極集電部材の作製］
　次に、負極集電部材２０を作製する。
　上述した如く、第１の金属層２１と、第１の金属層２１に拡散融合された第２の金属層２２とが一体化されたクラッド材からなる負極集電部材２０を作製する。クラッド材は、第１の金属層２１に形成される第１の金属薄板と、第２の金属層２２に形成される第２の金属薄板とを熱間圧延し、第１、第２の金属薄板を接合領域で金属拡散結合させることに作製する。このクラッド材をプレス加工して、内周側壁２０ａ、外周側壁２０ｂ、中間平坦部２０ｃおよび突起２０ｄを有する、図４（Ａ）、４（Ｂ）に図示された負極集電部材２０を形成する。 [Production of negative electrode current collector]
Next, the negative electrode current collecting member 20 is produced.
As described above, the negative electrode current collecting member 20 made of the clad material in which the first metal layer 21 and the second metal layer 22 diffused and fused to the first metal layer 21 are integrated is manufactured. The clad material is obtained by hot-rolling the first metal thin plate formed on the first metal layer 21 and the second metal thin plate formed on the second metal layer 22 to obtain the first and second metals. The thin plate is fabricated by metal diffusion bonding at the joining region. The clad material is pressed to form the negative electrode current collecting member 20 shown in FIGS. 4A and 4B having the inner peripheral side wall 20a, the outer peripheral side wall 20b, the intermediate flat portion 20c, and the protrusion 20d. .
〔発電ユニット作製〕
　負極集電部材２０の筒状凹部２９に軸芯１５の下端部を圧入し、軸芯１５の下端面を筒状凹部２９の底面に当接させる。この場合、軸芯１５の下端面を負極集電部材２０の筒状凹部２９の底面に当接することにより、負極集電部材２０の上下方向、換言すれば、軸方向の位置が定まる。
　次に、負極集電部材２０の外周側壁２０ｂの外周面に、負極タブ１７をほぼ均等に配分して密着し、負極集電部材２０に負極タブ１７を超音波溶接により接合する。この場合、上述した如く、負極集電部材２０の外周側壁２０ｂの外周面に負極タブ１７を密着させた状態で、負極タブ１７上にリボン４２を巻き付け、リボン４２上から溶接する。 [Production of power generation unit]
The lower end portion of the shaft core 15 is press-fitted into the cylindrical recess 29 of the negative electrode current collecting member 20, and the lower end surface of the shaft core 15 is brought into contact with the bottom surface of the cylindrical recess 29. In this case, by bringing the lower end surface of the shaft core 15 into contact with the bottom surface of the cylindrical recess 29 of the negative electrode current collecting member 20, the position of the negative electrode current collecting member 20 in the vertical direction, in other words, the axial direction is determined.
Next, the negative electrode tab 17 is almost uniformly distributed and adhered to the outer peripheral surface of the outer peripheral side wall 20b of the negative electrode current collecting member 20, and the negative electrode tab 17 is joined to the negative electrode current collecting member 20 by ultrasonic welding. In this case, as described above, with the negative electrode tab 17 in close contact with the outer peripheral surface of the outer peripheral side wall 20b of the negative electrode current collecting member 20, the ribbon 42 is wound around the negative electrode tab 17 and welded from above the ribbon 42.
　次に、軸芯１５の上端部の内側に正極集電部材３１の下部を圧入する。そして、正極電極１１の正極タブ１６を正極集電部材３１の周側壁の外面に密着させ、超音波溶接により正極タブ１６を溶接する。この場合、上述した如く、正極集電部材３１のリング状の周側面に正極タブ１６を密着させた状態で、正極タブ１６上にリボン４１を巻き付け、リボン４１上から溶接する。
　そして、正極導電リード３２の一端を正極集電部材３１の一面に超音波溶接等により接合する。但し、この段階では、正極導電リード３２は、非水電解液５の注入の障害とならないように、軸芯１５の中空部に対応する位置から外しておく。このようにして、発電ユニットが構成される。 Next, the lower portion of the positive electrode current collecting member 31 is press-fitted inside the upper end portion of the shaft core 15. And the positive electrode tab 16 of the positive electrode 11 is closely_contact | adhered to the outer surface of the surrounding side wall of the positive electrode current collection member 31, and the positive electrode tab 16 is welded by ultrasonic welding. In this case, as described above, with the positive electrode tab 16 in close contact with the ring-shaped peripheral side surface of the positive electrode current collector 31, the ribbon 41 is wound around the positive electrode tab 16 and welded from above the ribbon 41.
Then, one end of the positive electrode conductive lead 32 is joined to one surface of the positive electrode current collecting member 31 by ultrasonic welding or the like. However, at this stage, the positive electrode conductive lead 32 is removed from the position corresponding to the hollow portion of the shaft core 15 so as not to obstruct the injection of the non-aqueous electrolyte 5. In this way, the power generation unit is configured.
〔電池缶への収容〕
　一方、発電ユニットが収容可能な円筒状の電池缶２を絞り加工等により形成しておく。
　そして、上述の如く作製した発電ユニットを電池缶２内に収容する。 [Containment in battery can]
On the other hand, a cylindrical battery can 2 that can accommodate the power generation unit is formed by drawing or the like.
Then, the power generation unit manufactured as described above is accommodated in the battery can 2.
〔負極溶接〕
　電池缶２に収容された負極集電部材２０の突起２０ｄ周辺に対応する電池缶２の缶底２ｃを溶接用治具９１により支持する。次に、軸芯１５の中空部に電極棒９２を挿入する。この状態の断面図を図５に示す。
　電極棒９２の下端面を負極集電部材２０の筒状凹部２９の底部２９ａ上面、すなわち、第１の金属層２１の上面に押し付ける。これにより、負極集電部材２０の第２の金属層２２が電池缶２の缶底２ｃの内面に接触する。この状態で、電極棒９２および溶接用治具９１に通電し、負極集電部材２０を電池缶２の缶底２ｃに抵抗溶接等により接合する。抵抗溶接により、負極集電部材２０の突起２０ｄは溶融し、平坦となる。これに伴い、負極集電部材２０の筒状凹部２９の底部２９ａ全体、すなわち第２の金属層２２の底部が、電池缶２の缶底２ｃに接合される。 [Negative electrode welding]
The can bottom 2c of the battery can 2 corresponding to the periphery of the protrusion 20d of the negative electrode current collecting member 20 accommodated in the battery can 2 is supported by a welding jig 91. Next, the electrode rod 92 is inserted into the hollow portion of the shaft core 15. A cross-sectional view of this state is shown in FIG.
The lower end surface of the electrode bar 92 is pressed against the upper surface of the bottom 29 a of the cylindrical recess 29 of the negative electrode current collector member 20, that is, the upper surface of the first metal layer 21. As a result, the second metal layer 22 of the negative electrode current collecting member 20 comes into contact with the inner surface of the can bottom 2 c of the battery can 2. In this state, the electrode rod 92 and the welding jig 91 are energized, and the negative electrode current collecting member 20 is joined to the can bottom 2c of the battery can 2 by resistance welding or the like. By the resistance welding, the protrusion 20d of the negative electrode current collecting member 20 is melted and flattened. Accordingly, the entire bottom portion 29 a of the cylindrical recess 29 of the negative electrode current collecting member 20, that is, the bottom portion of the second metal layer 22 is joined to the can bottom 2 c of the battery can 2.
　上述した如く、第２の金属層２２は、第１の金属層２１の一面側の全面に亘り形成されており、接触面積が大きい。このため、第１の金属層２１と第２の金属層２２との接触抵抗を小さくすることができる。また、負極集電部材２０には、軸芯１５の中空部に対応する筒状凹部２９が形成されており、筒状凹部２９は、第１の金属層２１と、第２の金属層２２とが積層され、金属拡散結合されて形成されている。従って、ニッケル材からなる接続リードのみで電池缶２の缶底に接合されている従来の構造に比し、抵抗値を大幅に低減することができる。 As described above, the second metal layer 22 is formed over the entire surface of the first metal layer 21 and has a large contact area. For this reason, the contact resistance between the first metal layer 21 and the second metal layer 22 can be reduced. Further, the negative electrode current collecting member 20 is formed with a cylindrical concave portion 29 corresponding to the hollow portion of the shaft core 15, and the cylindrical concave portion 29 includes the first metal layer 21, the second metal layer 22, and the like. Are laminated and formed by metal diffusion bonding. Therefore, the resistance value can be greatly reduced as compared with the conventional structure in which the connection can made of the nickel material alone is joined to the bottom of the battery can 2.
［グルービング］
　次に、電池缶２の上端部側の一部をグルービングにより絞り内方に突出し、外面にほぼＵ字状の溝２ａを形成する。
〔電解液注入〕
　次に、電池缶２の内部に、非水電解液５を所定量注入する。
　非水電解液５は、軸芯１５の中空部の上部から注入される。軸芯１５の中空部の上部から注入された非水電解液５は、上述したように、軸芯１５の中空部を上部側から下部側に向けて流動し、軸芯１５の開口部１５ａ、負極集電部材２０の空隙部２６、開口２７の経路で軸芯１５内側から外側に流出する。電池缶２内への非水電解液５の注入が完了したら、正極導電リード３２を図５に点線で示すように折り返しておく。 [Grooving]
Next, a part on the upper end side of the battery can 2 protrudes inward of the diaphragm by grooving, and a substantially U-shaped groove 2a is formed on the outer surface.
[Injection of electrolyte]
Next, a predetermined amount of the non-aqueous electrolyte 5 is injected into the battery can 2.
The non-aqueous electrolyte 5 is injected from the upper part of the hollow portion of the shaft core 15. As described above, the non-aqueous electrolyte 5 injected from the upper part of the hollow part of the shaft core 15 flows from the upper part toward the lower part of the shaft core 15, and the opening 15 a of the shaft core 15. The negative electrode current collecting member 20 flows out from the inner side of the shaft core 15 through the path of the gap 26 and the opening 27. When the injection of the non-aqueous electrolyte 5 into the battery can 2 is completed, the positive electrode conductive lead 32 is folded back as shown by a dotted line in FIG.
〔正極溶接〕
　一方、上記工程とは別に、電池蓋３を導電接続板３３の周縁部にかしめて一体化しておく。
　電池缶２の溝２ａの上部にガスケット３４を収容する。このガスケット３４の上方に電池蓋３が固定された導電接続板３３を配置する。
　導電接続板３３を傾斜させ、一端が正極集電部材３１に溶接された正極導電リード３２の他端部をレーザ溶接等により導電接続板３３に接合する。 [Positive electrode welding]
On the other hand, separately from the above steps, the battery cover 3 is caulked and integrated with the periphery of the conductive connection plate 33.
A gasket 34 is accommodated in the upper part of the groove 2 a of the battery can 2. A conductive connection plate 33 to which the battery cover 3 is fixed is disposed above the gasket 34.
The conductive connection plate 33 is inclined, and the other end of the positive electrode conductive lead 32 whose one end is welded to the positive electrode current collecting member 31 is joined to the conductive connection plate 33 by laser welding or the like.
〔封口〕
　正極導電リード３２を導電接続板３３に接合した後は、電池蓋３が固定された導電接続板３３を水平にして、ガスケット３４上に配置する。
　この状態で、電池缶２の溝２ａと上端面の間の部分をプレスにより圧着するかしめ加工を行い、ガスケット３４と共に電池蓋３および導電接続板３３を電池缶２の開口部２ｂの周縁部に固定する。
　これにより、図１に図示された円筒形二次電池１が作製される。 [Sealing]
After joining the positive electrode conductive lead 32 to the conductive connection plate 33, the conductive connection plate 33 to which the battery cover 3 is fixed is placed horizontally and placed on the gasket 34.
In this state, caulking is performed by pressing the portion between the groove 2a and the upper end surface of the battery can 2 with a press, and the battery lid 3 and the conductive connection plate 33 together with the gasket 34 are attached to the peripheral portion of the opening 2b of the battery can 2. Fix it.
Thereby, the cylindrical secondary battery 1 illustrated in FIG. 1 is manufactured.
（実施形態２）
　図９は、本発明の円筒形二次電池の実施形態２を示す断面図であり、図１０（Ａ）は、図９に図示された負極集電部材の断面図であり、図１０（Ｂ）は、その底面図である。
　実施形態２が実施形態１と相違する点は、負極集電部材２０Ａが、リング状の外周側壁２０ｂ（図４（Ａ）参照）を有していない点である。
　すなわち、負極集電部材２０Ａは、筒状凹部２９の底部２９ａからほぼ垂直に立ち上がるリング状の内周側壁２０ａと、この内周側壁２０ａからほぼ垂直に屈曲された平坦な円盤状部２０ｃ1を有する形状に形成されている。負極集電部材２０Ａが、第１の金属層２１と、この第１の金属層に拡散融合された第２の金属層２２とが一体化されたクラッド材により形成されている構成は、実施形態１と同じである。 (Embodiment 2)
9 is a cross-sectional view showing Embodiment 2 of the cylindrical secondary battery of the present invention, and FIG. 10 (A) is a cross-sectional view of the negative electrode current collector shown in FIG. 9, and FIG. ) Is a bottom view thereof.
The difference between the second embodiment and the first embodiment is that the negative electrode current collecting member 20A does not have a ring-shaped outer peripheral side wall 20b (see FIG. 4A).
That is, the negative electrode current collecting member 20A has a ring-shaped inner peripheral side wall 20a that rises substantially perpendicularly from the bottom 29a of the cylindrical recess 29, and a flat disk-shaped part 20c1 that is bent substantially perpendicularly from the inner peripheral side wall 20a. It is formed into a shape. The configuration in which the negative electrode current collecting member 20A is formed of a clad material in which a first metal layer 21 and a second metal layer 22 diffused and fused to the first metal layer are integrated is an embodiment. Same as 1.
　実施形態２における負極集電部材２０Ａは、平坦な円盤状部２０ｃ1の下面全体に第２の金属層２２が形成された構造となっている。このため、負極電極１２の負極タブ１７は、負極集電部材２０Ａの円盤状部２０ｃ1の周縁部で第２の金属層２２に接合することになる。しかし、負極タブ１７の材料である銅系金属と、負極集電部材２０Ａの第２の金属層２２の材料であるニッケルとは、超音波溶接による接合が困難である。このため、実施形態２においては、負極タブ１７と負極集電部材２０Ａの第２の金属層２２との接合は、レーザ溶接による接合が推奨される。 The negative electrode current collecting member 20A in Embodiment 2 has a structure in which the second metal layer 22 is formed on the entire lower surface of the flat disk-shaped portion 20c1. For this reason, the negative electrode tab 17 of the negative electrode 12 is joined to the second metal layer 22 at the peripheral edge of the disc-like portion 20c1 of the negative electrode current collecting member 20A. However, the copper-based metal that is the material of the negative electrode tab 17 and the nickel that is the material of the second metal layer 22 of the negative electrode current collector 20A are difficult to join by ultrasonic welding. For this reason, in Embodiment 2, joining by the negative electrode tab 17 and the 2nd metal layer 22 of 20 A of negative electrode current collection members is recommended by laser welding.
　実施形態２においては、実施形態１に対して、外周側壁２０ｂを無くす分だけ面積を小さくすることができ、重量の軽減及びコスト低減を図ることができる。
　実施形態２における他の構成は実施形態１と同様であり、対応する部材に同一の符号を付してその説明を省略する。 In the second embodiment, compared to the first embodiment, the area can be reduced by eliminating the outer peripheral side wall 20b, and the weight can be reduced and the cost can be reduced.
Other configurations in the second embodiment are the same as those in the first embodiment, and the corresponding members are denoted by the same reference numerals and description thereof is omitted.
（実施形態３）
　図１１は、本発明の円筒形二次電池の実施形態３を示す断面図であり、図１２（Ａ）は、図１１に図示された負極集電部材の断面図であり、図１２（Ｂ）は、その底面図である。
　実施形態３が実施形態１と相違する点は、負極集電部材２０Ｂにおいて、第２の金属層２２が第１の金属層２１の一部の領域にのみ形成されている点である。
　すなわち、図１２（Ａ）、１２（Ｂ）に図示されるように、実施形態３における負極集電部材２０Ｂでは、第２の金属層２２は、筒状凹部２９の底部２９ａの直径より小さい幅で、負極集電部材２０Ｂの中心を通る直線状に、第１の金属層２１の一面側に形成されている。 (Embodiment 3)
FIG. 11 is a cross-sectional view showing Embodiment 3 of the cylindrical secondary battery of the present invention, and FIG. 12 (A) is a cross-sectional view of the negative electrode current collecting member shown in FIG. ) Is a bottom view thereof.
The third embodiment is different from the first embodiment in that the second metal layer 22 is formed only in a partial region of the first metal layer 21 in the negative electrode current collecting member 20B.
That is, as illustrated in FIGS. 12A and 12B, in the negative electrode current collector 20 </ b> B according to the third embodiment, the second metal layer 22 has a width smaller than the diameter of the bottom 29 a of the cylindrical recess 29. Thus, it is formed on one surface side of the first metal layer 21 in a straight line passing through the center of the negative electrode current collecting member 20B.
　この負極集電部材２０Ｂを作製するには、第１の金属層２１に形成される第１の金属薄板に、予め、第２の金属層２２に形成される第２の金属薄板を嵌合する溝を形成しておく。そして、第２の金属薄板を第１の金属薄板の溝に嵌合した状態で第１の金属薄板と、第２の金属薄板とを熱間圧延し、第１、第２の金属薄板を接合領域で金属拡散結合させ、クラッド材を作製する。この後は、実施形態１と同様に、クラッド材をプレス加工することにより、負極集電部材２０Ｂを形成する。 In order to produce this negative electrode current collecting member 20B, the second metal thin plate formed on the second metal layer 22 is fitted in advance to the first metal thin plate formed on the first metal layer 21. A groove is formed. Then, the first metal thin plate and the second metal thin plate are hot-rolled in a state where the second metal thin plate is fitted in the groove of the first metal thin plate, and the first and second metal thin plates are joined. A clad material is produced by metal diffusion bonding in the region. Thereafter, similarly to the first embodiment, the negative electrode current collecting member 20B is formed by pressing the clad material.
　実施形態３によれば、実施形態１よりも第２の金属層２２の面積を小さくすることができるので、コスト低減を図ることができる。
　実施形態３における他の構成は実施形態１と同様であり、対応する部材に同一の符号を付してその説明を省略する。 According to the third embodiment, since the area of the second metal layer 22 can be made smaller than that of the first embodiment, the cost can be reduced.
Other configurations in the third embodiment are the same as those in the first embodiment, and the corresponding members are denoted by the same reference numerals and description thereof is omitted.
（実施形態４）
　図１３は、本発明の円筒形二次電池の実施形態４を示す断面図であり、図１４（Ａ）は、図１３に図示された負極集電部材の断面図であり、図１４（Ｂ）は、その底面図である。
　実施形態４が実施形態３と相違する点は、負極集電部材２０Ｃが、リング状の外周側壁２０ｂ（図１２（Ａ）参照）を有していない点である。
　すなわち、負極集電部材２０Ｃは、筒状凹部２９の底部２９ａからほぼ垂直に立ち上がるリング状の内周側壁２０ａと、この内周側壁２０ａからほぼ垂直に屈曲された平坦な円盤状部２０ｃ2とを有する形状に形成されている。負極集電部材２０Ｃの第２の金属層２２が、筒状凹部２９の底部２９ａの直径より小さい幅で、負極集電部材２０Ｃの中心を通る直線状に、第１の金属層２１の一面側に形成されている点は実施形態３と同様である。 (Embodiment 4)
13 is a cross-sectional view showing Embodiment 4 of the cylindrical secondary battery of the present invention, and FIG. 14 (A) is a cross-sectional view of the negative electrode current collector shown in FIG. 13, and FIG. ) Is a bottom view thereof.
The difference between the fourth embodiment and the third embodiment is that the negative electrode current collecting member 20C does not have a ring-shaped outer peripheral side wall 20b (see FIG. 12A).
That is, the negative electrode current collecting member 20C includes a ring-shaped inner peripheral side wall 20a that rises substantially vertically from the bottom 29a of the cylindrical recess 29, and a flat disk-shaped portion 20c2 that is bent substantially vertically from the inner peripheral side wall 20a. It is formed in the shape to have. One surface side of the first metal layer 21 so that the second metal layer 22 of the negative electrode current collecting member 20C has a width smaller than the diameter of the bottom portion 29a of the cylindrical recess 29 and passes through the center of the negative electrode current collecting member 20C. This is the same as the third embodiment.
　実施形態４における負極集電部材２０Ｃは、平坦な円盤状部２０ｃ2の下面の一部に第２の金属層２２が形成された構造となっている。つまり、平坦な円盤状部２０ｃ2は、一部を除き、第１の金属層２１のみにより形成されている。このため、負極電極１２の負極タブ１７を、第２の金属層２２が形成されている部分を避け、第１の金属層２１が露出している領域上に寄せて配置することにより、負極タブ１７と負極集電部材２０Ｃとを、超音波溶接により接合することが可能となる。 The negative electrode current collecting member 20C in Embodiment 4 has a structure in which the second metal layer 22 is formed on a part of the lower surface of the flat disk-shaped portion 20c2. That is, the flat disk-shaped part 20c2 is formed of only the first metal layer 21 except for a part thereof. For this reason, the negative electrode tab 17 of the negative electrode 12 is disposed close to the region where the first metal layer 21 is exposed, avoiding the portion where the second metal layer 22 is formed, and thus the negative electrode tab 17 and the negative electrode current collecting member 20C can be joined by ultrasonic welding.
　実施形態４では、実施形態１に対して、外周側壁２０ｂを有しておらず、また、第２の金属層２２は第１の金属層２１の一部にしか形成されていない。従って、第２の金属層２２の面積を、実施形態２や３の場合よりも、さらに、小さいものとすることができる。
　実施形態４における他の構成は実施形態１と同様であり、対応する部材に同一の符号を付してその説明を省略する。 In the fourth embodiment, the outer peripheral side wall 20 b is not provided as compared with the first embodiment, and the second metal layer 22 is formed only on a part of the first metal layer 21. Therefore, the area of the second metal layer 22 can be made smaller than those in the second and third embodiments.
Other configurations in the fourth embodiment are the same as those in the first embodiment, and the corresponding members are denoted by the same reference numerals and description thereof is omitted.
（実施形態５）
　図１５、１６は本発明の円筒形二次電池の実施形態５を説明するための図であり、図１５（Ａ）は、円筒形二次電池の負極集電部材周辺部の断面図であり、図１６（Ａ）は、図１５（Ａ）に図示された負極集電部材の断面図であり、図１６（Ｂ）は、その底面図である。
　実施形態５は、実施形態３の場合と同様、負極集電部材２０Ｄにおいて、第２の金属層２２が第１の金属層２１の一部の領域に形成されている。しかし、実施形態５が実施形態３と相違する点は、第２の金属層２２が負極集電部材２０Ｄの中央領域のみでなく、中央領域を含む負極集電部材２０Ｄの半分以上の領域にわたり形成されている点である。
　すなわち、図１６（Ａ）、１６（Ｂ）に図示されるように、実施形態５における負極集電部材２０Ｄでは、第２の金属層２２は、負極集電部材２０Ｄにおける筒状凹部２９の中心から所定幅だけ食い込んだ位置に第１の金属層２１との境界部を有する。第２の金属層２２は、この境界部から、筒状凹部２９の中央に形成された突起２０ｄの領域を含め、負極集電部材２０Ｄの外周側壁２０ｂの端部までの全領域に亘り、第１の金属層２１の一面に形成されている。 (Embodiment 5)
FIGS. 15 and 16 are views for explaining Embodiment 5 of the cylindrical secondary battery of the present invention, and FIG. 15A is a cross-sectional view of the periphery of the negative electrode current collecting member of the cylindrical secondary battery. 16A is a cross-sectional view of the negative electrode current collector shown in FIG. 15A, and FIG. 16B is a bottom view thereof.
In the fifth embodiment, similarly to the third embodiment, the second metal layer 22 is formed in a partial region of the first metal layer 21 in the negative electrode current collecting member 20 </ b> D. However, the fifth embodiment is different from the third embodiment in that the second metal layer 22 is formed not only in the central region of the negative electrode current collecting member 20D but also in a region more than half of the negative electrode current collecting member 20D including the central region. It is a point that has been.
That is, as illustrated in FIGS. 16A and 16B, in the negative electrode current collector 20D according to Embodiment 5, the second metal layer 22 is the center of the cylindrical recess 29 in the negative electrode current collector 20D. A boundary portion with the first metal layer 21 is provided at a position where the first metal layer 21 has been cut in by a predetermined width. The second metal layer 22 extends over the entire region from this boundary portion to the end of the outer peripheral side wall 20b of the negative electrode current collecting member 20D, including the region of the protrusion 20d formed in the center of the cylindrical recess 29. It is formed on one surface of one metal layer 21.
　図１５（Ｂ）は負極集電部材２０Ｄ用の材料の平面図と断面図である。この材料を作製するには、第１の金属層２１に形成される第１の金属薄板に、予め、第２の金属層２２に形成される第２の金属薄板を嵌合する薄肉部を形成しておく。そして、第２の金属薄板を第１の金属薄板の薄肉部に嵌合した状態で第１の金属薄板と、第２の金属薄板とを熱間圧延し、第１、第２の金属薄板を接合領域で金属拡散結合させ、クラッド材を作製する。
この後は、実施形態３と同様に、クラッド材をプレス加工することにより、負極集電部材２０Ｄを形成する。 FIG. 15B is a plan view and a cross-sectional view of a material for the negative electrode current collecting member 20D. In order to fabricate this material, a thin portion for fitting the second metal thin plate formed on the second metal layer 22 is formed on the first metal thin plate formed on the first metal layer 21 in advance. Keep it. Then, the first metal thin plate and the second metal thin plate are hot-rolled in a state where the second metal thin plate is fitted to the thin portion of the first metal thin plate, and the first and second metal thin plates are A clad material is produced by metal diffusion bonding in the junction region.
Thereafter, similarly to the third embodiment, the negative electrode current collecting member 20D is formed by pressing the clad material.
　材料成形時、実施形態３では第２の金属薄板２２を第１の金属薄板２１の薄肉部に嵌合する際、両端が規制される為、嵌合幅の寸法公差を厳しくする必要が有る。これに対し、実施形態５の場合には、片側が規制されるのみである為、金属薄板２２の幅寸法公差が実質的に必要とされないものとなり、実施形態３に対し材料の製造工程を容易にすることができる。
　実施形態５における他の構成は実施形態３と同様であり、対応する部材に同一の符号を付してその説明を省略する。　 At the time of forming the material, in the third embodiment, when the second metal thin plate 22 is fitted to the thin portion of the first metal thin plate 21, both ends are restricted, so that it is necessary to tighten the dimensional tolerance of the fitting width. On the other hand, in the case of the fifth embodiment, since only one side is restricted, the width dimension tolerance of the thin metal plate 22 is not substantially required, and the material manufacturing process is easier than the third embodiment. Can be.
Other configurations in the fifth embodiment are the same as those in the third embodiment, and the corresponding members are denoted by the same reference numerals and description thereof is omitted.
以上説明した通り、本発明の各実施形態においては、負極集電部材２０、２０Ａ～２０Ｃを、正・負極のタブ１６、１７の一方が接続される第１の金属層２１と、第１の金属層２１に拡散融合され、電池缶２の缶底２ｃに接合される第２の金属層２２とが一体化したクラッド材により形成した。このため、第１の金属層２１と、第２の金属層２２の接触領域が全面接触となり、第１、第２の金属層２１、２２の接触抵抗を低減することができる。第１、第２の金属の接触抵抗が低減するので、高価な第２の金属の厚さを薄くすることができ、コストを低減することができる。 As described above, in each embodiment of the present invention, the negative electrode current collector members 20 and 20A to 20C are connected to the first metal layer 21 to which one of the positive and negative electrode tabs 16 and 17 is connected, The clad material was formed by diffusion fusion with the metal layer 21 and the second metal layer 22 joined to the can bottom 2 c of the battery can 2. For this reason, the contact area of the 1st metal layer 21 and the 2nd metal layer 22 becomes a whole surface contact, and the contact resistance of the 1st, 2nd metal layers 21 and 22 can be reduced. Since the contact resistance of the first and second metals is reduced, the thickness of the expensive second metal can be reduced, and the cost can be reduced.
　実施形態２および４のように、外周側壁２０ｂを無くし、平坦にすれば、高価な第２の金属層２２の面積をより小さくすることができる。 As in Embodiments 2 and 4, the area of the expensive second metal layer 22 can be made smaller by eliminating the outer peripheral side wall 20b and making it flat.
　実施形態３および４のように、第２の金属層２２を第１の金属層２１の面積より小さくすれば、高価な第２の金属層２２の面積をより小さくすることができる。 If the second metal layer 22 is made smaller than the area of the first metal layer 21 as in the third and fourth embodiments, the area of the expensive second metal layer 22 can be made smaller.
　実施形態５のように、第２の金属層２２を、負極集電部材２０Ｄの中心を含んで負極集電部材２０Ｄの外周側部２０ｂの端部まで、平面視で円形状の第２の金属層２２の半分以上の領域に形成するようにすれば、材料費の低減と共に生産性の向上を図ることができる。 As in the fifth embodiment, the second metal layer 22 is formed in a circular shape in plan view from the center of the negative electrode current collector 20D to the end of the outer peripheral side 20b of the negative electrode current collector 20D. If the layer 22 is formed in more than half of the region 22, the material cost can be reduced and the productivity can be improved.
　軸芯１５が嵌合される負極集電部材２０、２０Ａ～２０Ｃの筒状凹部２９に、軸芯１５の外周に接触する複数の突出部２５を設け、各突出部２５の間に、空隙部２６が形成されるようにしたので、非水電解液５の流動性を確保することができる。 A plurality of protrusions 25 that come into contact with the outer periphery of the shaft core 15 are provided in the cylindrical recesses 29 of the negative electrode current collecting members 20 and 20A to 20C to which the shaft core 15 is fitted. Since 26 is formed, the fluidity of the non-aqueous electrolyte 5 can be ensured.
　負極集電部材２０、２０Ａ～２０Ｃの内周側壁２０ａの各空隙部２６に対応する位置に、開口２７を設けたので、非水電解液５の流動性が確保され、かつ、過充電等により発生するガスのガス抜きを良好にすることができる。 Since the opening 27 is provided at a position corresponding to each gap portion 26 of the inner peripheral side wall 20a of the negative electrode current collecting member 20, 20A to 20C, the fluidity of the non-aqueous electrolyte 5 is ensured, and overcharge or the like is performed. Degassing of the generated gas can be improved.
　上記実施形態では、第２の金属層２２をニッケルで形成する場合、その板厚を０．２ｍｍ～０．７ｍｍ程度としたので、電池缶２との接合力を満足し、かつ、抵抗値が小さい特性部分が効率的に活用され、特性の良好な円筒形二次電池１を形成することができる。 In the above embodiment, when the second metal layer 22 is formed of nickel, the plate thickness is set to about 0.2 mm to 0.7 mm, so that the joining force with the battery can 2 is satisfied and the resistance value is A small characteristic part is efficiently utilized, and the cylindrical secondary battery 1 having good characteristics can be formed.
　なお、上記各実施形態では、第１の金属層２１を銅または銅合金とし、第２の金属層２２をニッケルとした場合で例示した。しかし、第１の金属層２１、第２の金属層２２は、これに限られるものではない。電池缶２がステンレスで形成されている場合には、第２の金属層２２をステンレスとし、電池缶２がアルミニウムで形成されている場合には、第２の金属層２２をアルミニウムまたはアルミニウム合金とすることができる。要は、第２の金属層２２を構成する金属材料として、第１の金属層２１よりも電池缶２との接合力が大きいものを用いればよい。 In each of the above embodiments, the first metal layer 21 is made of copper or a copper alloy, and the second metal layer 22 is made of nickel. However, the first metal layer 21 and the second metal layer 22 are not limited to this. When the battery can 2 is made of stainless steel, the second metal layer 22 is made of stainless steel. When the battery can 2 is made of aluminum, the second metal layer 22 is made of aluminum or an aluminum alloy. can do. In short, as the metal material constituting the second metal layer 22, a material having a larger bonding force with the battery can 2 than the first metal layer 21 may be used.
　上記実施形態では、リチウムイオン円筒形二次電池の場合で説明した。しかし、本発明は、ニッケル水素電池またはニッケル・カドミウム電池、鉛蓄電池のように水溶性電解液を用いる円筒形二次電池にも適用が可能である。 In the above embodiment, the case of a lithium ion cylindrical secondary battery has been described. However, the present invention can also be applied to a cylindrical secondary battery using a water-soluble electrolyte such as a nickel metal hydride battery, a nickel cadmium battery, or a lead storage battery.
　上記実施形態では、負極集電部材２０を電池缶２に接合する電池缶側が負極の場合で例示した。しかし、本発明は、正極集電部材３１を電池缶２に接合する電池缶側が正極の場合にも、電池缶と集電部材との接続構造は同じであるため適用することができる。 In the above embodiment, the case where the negative electrode current collecting member 20 is joined to the battery can 2 is the negative electrode. However, the present invention can also be applied to the case where the battery can side that joins the positive electrode current collecting member 31 to the battery can 2 is the positive electrode because the connection structure between the battery can and the current collecting member is the same.
　その他、本発明の円筒形二次電池は、発明の趣旨の範囲内において、種々、変形して適用することが可能であり、要は、負極集電部材２０、２０Ａ～２０Ｃを、正・負極のタブ（電極タブ）１６、１７の一方が接続される第１の金属層２１と、第１の金属層２１に拡散融合され、電池缶２の缶底２ｃに接合される第２の金属層２２とが一体化したクラッド材により形成するようにしたものであればよい。 In addition, the cylindrical secondary battery of the present invention can be applied with various modifications within the scope of the invention. In short, the negative electrode current collecting members 20, 20A to 20C are connected to the positive and negative electrodes. The first metal layer 21 to which one of the tabs (electrode tabs) 16 and 17 is connected, and the second metal layer which is diffused and fused to the first metal layer 21 and joined to the can bottom 2c of the battery can 2 What is necessary is just to form it by the clad material with which 22 was integrated.
　次の優先権基礎出願の開示内容は引用文としてここに組み込まれる。
　ＰＣＴ／ＪＰ２０１１／０６８６９１（２０１１年８月１８日出願） The disclosure of the following priority application is hereby incorporated by reference.
PCT / JP2011-068691 (filed on August 18, 2011)

Claims (9)

  1. 　円筒状の軸芯の周囲に、正極電極と負極電極とをセパレータを介して捲回した電極群と、
    　上部側に開口部を有し、前記電極群が収容されると共に電解液が注入された電池缶と、
    　前記電池缶の上部側に配置された電池蓋と、
    　前記電池缶の缶底と前記軸芯の下端部との間に配置され、前記負極電極の負極タブが接続されると共に前記電池缶に接合された負極集電部材とを備え、
    　前記負極集電部材は、前記負極電極が接続される第１の金属と、前記第１の金属に拡散融合され、前記電池缶の缶底に接合された第２の金属とが一体化したクラッド材により形成され、
    　前記第１の金属は、銅または銅合金で形成され、
    　前記第２の金属はニッケルで形成され
    　前記負極集電部材は、外周側に外周側壁を有するリング状であり、
    　前記負極集電部材は、中央部に前記軸芯の先端部側が挿入される筒状凹部が形成され、
    　前記筒状凹部において、前記第２の金属は前記電池缶の缶底に接合され、
    　前記負極集電部材の外周側壁において、前記負極タブは前記第１の金属に超音波溶接により接合されている円筒形二次電池。     Around the cylindrical shaft core, an electrode group in which a positive electrode and a negative electrode are wound through a separator,
    A battery can having an opening on the upper side, in which the electrode group is accommodated and an electrolyte is injected,
    A battery lid disposed on the upper side of the battery can;
    A negative electrode current collecting member disposed between the bottom of the battery can and the lower end of the shaft core, and connected to the negative electrode tab of the negative electrode and joined to the battery can;
    The negative electrode current collector member is a clad in which a first metal to which the negative electrode is connected and a second metal that is diffused and fused to the first metal and joined to the bottom of the battery can Formed by the material,
    The first metal is formed of copper or a copper alloy;
    The second metal is formed of nickel, and the negative electrode current collector is a ring having an outer peripheral side wall on the outer peripheral side,
    The negative electrode current collector member is formed with a cylindrical recess into which the tip end side of the shaft core is inserted at the center,
    In the cylindrical recess, the second metal is joined to the bottom of the battery can,
    A cylindrical secondary battery in which the negative electrode tab is joined to the first metal by ultrasonic welding on an outer peripheral side wall of the negative electrode current collecting member.
  2. 　請求項１に記載の円筒形二次電池において、
    　前記第２の金属は、前記第１の金属の一面側の全面に拡散融合されている円筒形二次電池。     The cylindrical secondary battery according to claim 1,
    The cylindrical secondary battery in which the second metal is diffused and fused to the entire surface of the first metal on one side.
  3. 　請求項１または２に記載の円筒形二次電池において、
    　前記第２の金属は、０．２～０．７ｍｍ程度の厚さを有する円筒形二次電池。     The cylindrical secondary battery according to claim 1 or 2,
    The second metal is a cylindrical secondary battery having a thickness of about 0.2 to 0.7 mm.
  4. 　請求項１に記載の円筒形二次電池において、
    前記集電部材の前記筒状凹部には、前記軸芯の外周に接触する複数の突出部が形成されている円筒形二次電池。     The cylindrical secondary battery according to claim 1,
    A cylindrical secondary battery in which a plurality of protrusions that are in contact with the outer periphery of the shaft core are formed in the cylindrical recess of the current collecting member.
  5. 　請求項４に記載の円筒形二次電池において、
    　前記筒状凹部の前記突出部間には、前記軸芯の外周から離間する空隙部が形成されると共に、
    　前記筒状凹部の突出部間には、前記筒状凹部の内側から外側に貫通する開口が形成されている円筒形二次電池。     The cylindrical secondary battery according to claim 4,
    Between the protrusions of the cylindrical recess, a gap is formed that is separated from the outer periphery of the shaft core, and
    A cylindrical secondary battery in which an opening penetrating from the inside to the outside of the cylindrical recess is formed between the protruding portions of the cylindrical recess.
  6. 　請求項１に記載の円筒形二次電池において、
    　前記第２の金属は、前記第１の金属の一面側において、前記凹状筒部の中心を含む一部の領域に形成されている円筒形二次電池。     The cylindrical secondary battery according to claim 1,
    The second metal is a cylindrical secondary battery formed in a partial region including the center of the concave cylindrical portion on one surface side of the first metal.
  7. 　請求項６に記載の円筒形二次電池において、前記第２の金属は、前記凹状筒部の幅よりも小さい幅で、前記負極集電部材の外周側壁の一端側から他端側に直線状に形成されている円筒形二次電池。 The cylindrical secondary battery according to claim 6, wherein the second metal has a width smaller than a width of the concave cylindrical portion and is linear from one end side to the other end side of the outer peripheral side wall of the negative electrode current collector. Cylindrical secondary battery formed in.
  8. 　請求項６に記載の円筒形二次電池において、前記第２の金属は、リング状の前記負極集電部材の中心を含んで、前記外周側壁の端部まで、平面視で前記負極集電部材の半分以上の領域に形成されている円筒形二次電池。 7. The cylindrical secondary battery according to claim 6, wherein the second metal includes the center of the ring-shaped negative electrode current collector and extends to the end of the outer peripheral side wall in plan view. Cylindrical secondary battery formed in more than half of the area.
  9. 　請求項１乃至８のいずれか１項に記載の円筒形二次電池において、前記筒状凹部の底面に前記電池缶の缶底側に向かって突き出す突起が形成され、前記第２の金属は、前記突起の前記缶底側に対面する表面に形成されている円筒形二次電池。 The cylindrical secondary battery according to any one of claims 1 to 8, wherein a protrusion protruding toward the bottom of the battery can is formed on a bottom surface of the cylindrical recess, and the second metal is A cylindrical secondary battery formed on a surface of the protrusion facing the bottom of the can.
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