WO2020262437A1 - 円筒形非水電解質二次電池 - Google Patents
円筒形非水電解質二次電池 Download PDFInfo
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- WO2020262437A1 WO2020262437A1 PCT/JP2020/024745 JP2020024745W WO2020262437A1 WO 2020262437 A1 WO2020262437 A1 WO 2020262437A1 JP 2020024745 W JP2020024745 W JP 2020024745W WO 2020262437 A1 WO2020262437 A1 WO 2020262437A1
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- positive electrode
- lead
- secondary battery
- insulating plate
- aqueous electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
- H01M50/593—Spacers; Insulating plates
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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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/172—Arrangements of electric connectors penetrating the casing
- H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
- H01M50/179—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for cells having curved cross-section, e.g. round or elliptic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/186—Sealing members characterised by the disposition of the sealing members
- H01M50/188—Sealing members characterised by the disposition of the sealing members the sealing members being arranged between the lid and terminal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/30—Arrangements for facilitating escape of gases
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
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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
- H01M2200/00—Safety devices for primary or secondary batteries
- H01M2200/20—Pressure-sensitive devices
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 disclosure relates to a cylindrical non-aqueous electrolyte secondary battery.
- an upper insulating plate having a central hole is arranged on the electrode group in order to prevent a short circuit due to contact between the positive electrode lead and the electrode group. Is being done.
- the center hole penetrates the central part of the upper insulating plate, and the high-pressure gas generated inside the secondary battery is discharged through the upper insulating plate, or the electrolytic solution is injected into the electrode group side. Used.
- the electrode group is arranged inside the outer can, and one end of the outer can is closed with a sealing body.
- Patent Document 1 describes a cylindrical secondary battery having an upper insulating plate, which is a central hole, a lead hole through which a positive electrode lead penetrates, and a plurality of openings formed in a half portion on the opposite side of the lead hole.
- the configuration having and is disclosed.
- the lead hole has a substantially semicircular arc shape in a plan view, and has two straight lines extending in a substantially radial direction at both ends in the circumferential direction.
- the positive electrode lead may be led out from one end of the lead hole of the upper insulating plate in the arc direction to the sealing body side.
- the conductive portion of the positive electrode lead faces the electrode group via the other end in the arc direction of the lead hole. It will be easier. Therefore, when the secondary battery is manufactured, the one that may cause a short circuit in the future is discharged as a manufacturing defect depending on the bending position of the positive electrode lead with respect to the central portion of the upper insulating plate, and the manufacturing cost of the battery increases.
- An object of the present disclosure is to provide a cylindrical non-aqueous electrolyte secondary battery capable of effectively preventing a short circuit between the electrode group and the positive electrode lead due to a variation in the bending position of the positive electrode lead with respect to the insulating plate.
- the cylindrical non-aqueous electrolyte secondary battery according to the present disclosure includes an outer can, a sealing body that closes one end of the outer can, an electrode group arranged inside the outer can, and insulation arranged between the sealing body and the electrode group. It is a cylindrical non-aqueous electrolyte secondary battery provided with a plate.
- a positive electrode and a negative electrode are spirally wound via a separator, and an insulating plate is a lead through which a positive electrode lead led out from the electrode group penetrates.
- It has a disk shape with a hole and a central hole penetrating the central portion, and the outer edge of the lead hole is a curved portion arranged along an arc concentric with the outer peripheral circle of the insulating plate in a plan view, and the arc. It is a cylindrical non-aqueous electrolyte secondary battery including a straight portion arranged along a string connecting both ends of the battery.
- cylindrical non-aqueous electrolyte secondary battery it is possible to effectively prevent a short circuit between the electrode group and the positive electrode lead due to the variation in the bending position of the positive electrode lead with respect to the insulating plate.
- FIG. 1 is a schematic cross-sectional view of a cylindrical non-aqueous electrolyte secondary battery of an example of the embodiment.
- FIG. 2 is a diagram schematically showing a portion closer to the inner end in the winding direction in the electrode group of the AA cross section of FIG.
- FIG. 3 is a diagram showing the facing relationship between the positive electrode and the negative electrode by expanding the portion of the electrode group shown in FIG. 2 near the inner end in the winding direction.
- FIG. 4 is a schematic view seen from above of FIG.
- FIG. 5A is a plan view of the upper insulating plate shown in FIG.
- FIG. 5B is an enlarged view of part B of FIG. 5A.
- FIG. 6 shows the positive electrode lead and the lead hole when the upper insulating plate is viewed from above when the positive electrode lead is led out from the circumferential center position of the lead hole in the cylindrical non-aqueous electrolyte secondary battery of the comparative example. It is a figure which shows the positional relationship with.
- FIG. 7 is a diagram corresponding to FIG. 6 in the case where the positive electrode lead is led out from one end in the circumferential direction of the lead hole in the cylindrical non-aqueous electrolyte secondary battery of the comparative example.
- FIG. 8 is a diagram showing a difference between the lead hole shape of the upper insulating plate of the embodiment and the lead hole shape of the comparative example.
- FIG. 9 is a diagram corresponding to FIG. 7 in the embodiment.
- FIG. 10 is a diagram corresponding to FIG. 5 in the upper insulating plate according to the cylindrical non-aqueous electrolyte secondary battery of Experimental Example 3.
- FIG. 11 compares the shape of the upper insulating plate, the aperture ratio with respect to the area in the outer circle of the upper insulating plate, and the burst rate of the battery case in the cylindrical non-aqueous electrolyte secondary batteries according to Experimental Examples 1 to 4. It is a figure.
- FIG. 12 is a diagram corresponding to FIG. 1 in another example of the embodiment.
- FIG. 13 is a diagram corresponding to FIG. 7 in another example of the embodiment.
- FIG. 1 is a schematic cross-sectional view of the cylindrical non-aqueous electrolyte secondary battery 10 of the embodiment.
- FIG. 2 is a diagram schematically showing a portion of the electrode group 14 in the AA cross section of FIG. 1 near the inner end in the winding direction.
- the cylindrical non-aqueous electrolyte secondary battery 10 includes a wound electrode group 14 and a non-aqueous electrolyte (not shown).
- the electrode group 14 has a positive electrode 11, a negative electrode 12, and a separator 13, and the positive electrode 11 and the negative electrode 12 are spirally wound via the separator 13.
- FIG. 1 is a schematic cross-sectional view of the cylindrical non-aqueous electrolyte secondary battery 10 of the embodiment.
- FIG. 2 is a diagram schematically showing a portion of the electrode group 14 in the AA cross section of FIG. 1 near the inner end in the winding direction.
- the cylindrical non-aqueous electrolyte secondary battery 10 includes a wound electrode group 14 and a non-a
- FIG. 1 shows the shape of the electrode group 14 as seen from the outer peripheral side.
- one side of the electrode group 14 in the winding axis direction may be referred to as “upper”, and the other side in the winding axis direction may be referred to as “lower”.
- the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
- the non-aqueous electrolyte is not limited to the liquid electrolyte, and may be a solid electrolyte using a gel polymer or the like.
- the cylindrical non-aqueous electrolyte secondary battery 10 will be referred to as a secondary battery 10.
- the positive electrode 11, the negative electrode 12, and the separator 13 constituting the electrode group 14 are all formed in a band shape, and are wound in a spiral shape so that the electrode group 14 is alternately laminated in the radial direction.
- the longitudinal direction of each electrode is the winding direction
- the width direction of each electrode is the winding axis direction.
- the positive electrode lead 16 that electrically connects the positive electrode 11 and the positive electrode terminal is provided at substantially the center of, for example, the winding inner end portion and the winding outer end portion of the electrode group 14, and is provided in the electrode group 14. It is derived from the upper end (upper side of FIG. 1) in the winding axis direction ⁇ .
- the negative electrode lead 40 (FIG.
- the positive electrode lead 16 and the negative electrode lead 40 are rectangular strip-shaped conductive members having a thickness larger than that of the electrode core.
- the thickness of each lead is, for example, 3 to 30 times the thickness of the core body, and is generally 50 ⁇ m to 500 ⁇ m.
- the constituent material of each reed is not particularly limited.
- the positive electrode lead 16 is preferably composed of a metal containing aluminum as a main component
- the negative electrode lead is preferably composed of a metal containing nickel or copper as a main component, or a metal containing both nickel and copper.
- the negative electrode 12 is not exposed on the outermost peripheral surface of the electrode group 14, but the negative electrode lead is joined to the end of the negative electrode core on the winding end side, and the negative electrode lead is attached to the lower end of the electrode group 14 in the winding axis direction ⁇ (FIG. 1). It may be led out from the lower side) and joined to the bottom of the outer can 20 together with the negative electrode lead 40.
- the positive electrode 11 and the negative electrode 12 will be described in more detail.
- the positive electrode 11 has a band-shaped positive electrode core body and a positive electrode mixture layer formed on the core body.
- positive electrode mixture layers are formed on both sides of the positive electrode core body.
- a metal foil such as aluminum, a film on which the metal is arranged on the surface layer, or the like is used.
- a suitable positive electrode core is a metal foil containing aluminum or an aluminum alloy as a main component.
- the thickness of the positive electrode core is, for example, 10 ⁇ m to 30 ⁇ m.
- the positive electrode mixture layer is formed on both sides of the positive electrode core body over the entire area except the plain portion to which the positive electrode leads are joined.
- the positive electrode mixture layer preferably contains a positive electrode active material, a conductive agent, and a binder.
- the positive electrode shall be dried and rolled after applying a positive electrode mixture slurry containing a positive electrode active material, a conductive agent, a binder, and a solvent such as N-methyl-2-pyrrolidone (NMP) on both sides of the positive electrode core. Is made by.
- the positive electrode active material examples include lithium-containing transition metal oxides containing transition metal elements such as Co, Mn, and Ni.
- the lithium-containing transition metal oxide is not particularly limited, but the general formula Li 1 + x MO 2 (in the formula, -0.2 ⁇ x ⁇ 0.2, M contains at least one of Ni, Co, Mn, and Al). It is preferably a composite oxide represented by.
- Examples of the above-mentioned conductive agent include carbon materials such as carbon black (CB), acetylene black (AB), Ketjen black, and graphite.
- Examples of the binder include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide (PI), acrylic resins, and polyolefin resins. Be done. Further, these resins may be used in combination with carboxymethyl cellulose (CMC) or a salt thereof, polyethylene oxide (PEO) and the like. One of these may be used alone, or two or more of them may be used in combination.
- CMC carboxymethyl cellulose
- PEO polyethylene oxide
- the negative electrode 12 has a band-shaped negative electrode core body and a negative electrode mixture layer formed on the negative electrode core body.
- a negative electrode mixture layer is formed on both sides of the negative electrode core body.
- a metal foil such as copper, a film on which the metal is arranged on the surface layer, or the like is used.
- the thickness of the negative electrode core is, for example, 5 ⁇ m to 30 ⁇ m.
- the negative electrode mixture layer can be formed on both sides of the negative electrode core body in almost the entire area except the plain portion to which the negative electrode leads 40 are bonded.
- the negative electrode mixture layer preferably contains a negative electrode active material and a binder.
- the negative electrode 12 is produced by applying, for example, a negative electrode mixture slurry containing a negative electrode active material, a binder, water, and the like to both surfaces of a negative electrode core, and then drying and rolling.
- the negative electrode active material is not particularly limited as long as it can reversibly occlude and release lithium ions, for example, a carbon material such as natural graphite or artificial graphite, a metal alloying with lithium such as Si or Sn, or these. Alloys containing, composite oxides and the like can be used.
- the binder contained in the negative electrode mixture layer for example, the same resin as in the case of the positive electrode 11 is used.
- SBR styrene-butadiene rubber
- CMC styrene-butadiene rubber
- polyacrylic acid or a salt thereof, polyvinyl alcohol and the like can be used. One of these may be used alone, or two or more of them may be used in combination.
- FIG. 3 is a diagram showing the facing relationship between the positive electrode 11 and the negative electrode 12 by expanding the portion of the electrode group 14 shown in FIG. 2 near the inner end in the winding direction.
- FIG. 4 is a schematic view seen from above of FIG. As shown in FIGS. 2 to 4, only the negative electrode 12 of the positive electrode 11 and the negative electrode 12 is arranged at the winding start portion of the electrode group 14. Specifically, the negative electrode 12 is wound around 1.25 turns or more from the inner end in the winding direction (point E1 in FIG. 2), which is the winding start end of the electrode group 14, via the separator 13 without facing the positive electrode 11. Also includes a non-opposing portion 12a.
- point E1 in FIG. 2 point E1 in FIG. 2
- the negative electrode 12 is continuously wound from the non-opposing portion 12a wound 1.5 times from the inner end E1 in the winding direction and from the non-opposing portion 12a, and faces the positive electrode 11 via the separator 13. Includes the facing portion 12b.
- the non-opposing portion 12a is a portion of the negative electrode 12 shown in FIG. 2 from the inner end E1 in the winding direction to the point E2 along the winding direction.
- the straight line passing through E2 is drawn so that the shortest distance is from the inner end of the positive electrode 11 in the winding direction to the negative electrode 12 inside the winding direction, and the intersection E2 between the straight line and the negative electrode 12 is the non-opposing portion 12a. Corresponds to the outer end of the winding direction. Further, the straight line passing through E1 is drawn so as to be arranged on an extension of the straight line passing through E2.
- the non-opposing portion 12a has a negative electrode mixture layer forming portion 12c and a negative electrode core body exposed portion 12d.
- the negative electrode mixture layer forming portion 12c is a portion in which the negative electrode mixture layer is formed on at least one surface of the non-opposing portion 12a continuously inward in the winding direction from the outer end in the winding direction (point E2 in FIG. 2).
- the negative electrode core body exposed portion 12d is a portion of the non-opposing portion 12a that is continuous from the inner end in the winding direction (point E1 in FIG. 2) to the outside in the winding direction and in which the negative electrode mixture layer is not formed on both sides.
- the negative electrode core body exposed portion 12d is shown by a thin solid line
- the negative electrode mixture layer forming portion 12c is shown by a thick solid line.
- the negative electrode mixture layer forming portion 12c is wound around 0.75 turns or more.
- the case where the negative electrode mixture layer forming portion 12c is wound 0.8 times is shown.
- the outer can 20 which is a bottomed cylindrical metal container and the sealing body 22 constitute a battery case 18 for accommodating the electrode group 14 and the non-aqueous electrolyte.
- the sealing body 22 closes the open end portion of the outer can 20.
- a gasket 24 is provided between the outer can 20 and the sealing body 22 to ensure the airtightness inside the battery case 18.
- the outer can 20 has, for example, an overhanging portion 21 that supports the sealing body 22 formed by pressing a side surface portion from the outside.
- the overhanging portion 21 is preferably formed in an annular shape along the circumferential direction of the outer can 20, and the sealing body 22 is supported on the upper surface thereof.
- the sealing body 22 is schematically shown in the shape of a disk having a rectangular cross section.
- the sealing body 22 has a configuration having an internal pressure actuated safety valve.
- the sealing body 22 is composed of a filter, a lower valve body, an insulating member, an upper valve body, and a cap, which are laminated in order from the electrode group 14 side.
- Each member constituting the sealing body 22 has, for example, a disk shape or a ring shape, and each member except the insulating member is electrically connected to each other.
- the lower valve body and the upper valve body are connected to each other at the central portion thereof, and an insulating member is interposed between the peripheral portions thereof.
- the lower valve body breaks, which causes the upper valve body to swell toward the cap side and separate from the lower valve body, thereby establishing an electrical connection between the two. It is blocked.
- the upper valve body breaks and the gas generated inside is released through the opening formed in the cap.
- the upper valve body and the lower valve body form an exhaust valve.
- An upper insulating plate 26 is arranged between the sealing body 22 and the electrode group 14.
- the upper insulating plate 26 is shown so as to be separated from the electrode group 14, but the upper insulating plate 26 is actually arranged so as to be in contact with the upper end of the electrode group 14.
- the positive electrode lead 16 is a conductive member for electrically connecting the positive electrode core body and the positive electrode terminal, and is led out from the upper end of the electrode group 14 to one side (upper side of FIG. 1) of the winding axis direction ⁇ of the electrode group 14. ing.
- One end of the positive electrode lead 16 is joined to, for example, a portion of the positive electrode core body located at a substantially central portion in the radial direction ⁇ of the electrode group 14. Further, the other end (upper end of FIG.
- the positive electrode lead 16 is joined near the center of the lower surface of the sealing body 22. In this state, the positive electrode lead 16 extends to the sealing body 22 side through the lead hole 27 described later of the upper insulating plate 26. In the secondary battery 10, the top plate of the sealing body 22 or the cap located at the upper end serves as the positive electrode terminal.
- the positive electrode lead 16 derived from the electrode group 14 is placed so as to overlap the sealing body 22. Then, the positive electrode lead 16 is welded to the sealing body 22 by laser welding or the like. An insulating tape is attached to the portion of the positive electrode lead 16 that is derived from the electrode group 14 on the electrode group 14 side.
- FIG. 1 shows a portion to which the insulating tape is attached by the oblique grid portion of the positive electrode lead 16. Therefore, of the lead-out portion of the positive electrode lead 16, the plain portion of FIG. 1 is an exposed portion of the conductive portion exposed from the insulating tape.
- the sealing body 22 is attached to the open end portion of the outer can 20.
- the positive electrode lead 16 is bent toward the upper insulating plate 26 at a position adjacent to the lead hole 27 to form the first curved portion 16a.
- the positive electrode lead 16 is folded back at a position opposite to the first curved portion 16a with respect to the central axis O of the secondary battery 10 orthogonal to the sealing body 22 to form the second curved portion 16b.
- the insulating tape is provided within a range not exceeding the inflection point of the second curved portion 16b from the electrode group 14 side to the sealing body 22 side of the positive electrode lead 16 so as not to hinder the welding of the sealing body 22 and the positive electrode lead 16.
- the insulating tape may be attached not only to the portion of the positive electrode lead 16 led out from the electrode group 14, but also to a part of the portion arranged inside the electrode group 14, and the surface facing the upper insulating plate 26 may be attached. It may be attached only to. Further, the insulating tape may be attached to the positive electrode lead 16 so as to be spirally wound around the diagonal lattice portion of FIG.
- the secondary battery 10 may be deformed so as to be compressed in the central axis O direction in a crush test or the like.
- the central axis O direction of the secondary battery 10 coincides with the winding axis direction ⁇ of the electrode group 14.
- the upper insulating plate 26 has a lead hole 27 through which the positive electrode lead 16 penetrates as described later, depending on the shape of the lead hole 27, the exposed portion of the positive electrode lead 16 from the insulating tape through the lead hole 27. May come into contact with the electrode group 14 and cause a short circuit.
- the shape of the lead hole 27 is regulated as described later.
- a lower insulating plate (not shown) is arranged between the lower end of the electrode group 14 and the bottom of the outer can 20.
- a through hole is formed in the center of the lower insulating plate.
- the negative electrode lead 40 (FIG. 3) having one end joined to the negative electrode core is led out to the lower side of the lower insulating plate through the through hole of the lower insulating plate or the outer peripheral side of the lower insulating plate, and is led out to the lower side of the lower insulating plate. Is joined by welding.
- FIG. 5A is a plan view of the upper insulating plate 26.
- FIG. 5B is an enlarged view of part B of FIG. 5A.
- the upper insulating plate 26 has a small disc shape.
- the upper insulating plate 26 is formed of an insulating material such as a polyolefin resin.
- the polyolefin-based resin is preferable from the viewpoint of reducing the manufacturing cost, and for example, a polypropylene resin can be used as the polyolefin-based resin.
- the upper insulating plate 26 is used to prevent a short circuit between the electrode group 14 and the positive electrode lead 16 or the like derived from the electrode group 14. Therefore, it is preferable that the upper insulating plate 26 covers almost the entire upper end of the electrode group 14. Therefore, the outer diameter d1 (FIG. 5A) of the upper insulating plate 26 matches the inner diameter d2 (FIG. 1) of the outer can 20 before the use of the secondary battery 10, or is inserted into the outer can 20 at the time of assembly. It is slightly smaller than the inner diameter d2 in consideration of the property.
- the outer diameter d1 of the upper insulating plate 26 is preferably 98% or more and 100% or less, and more preferably 98% or more and 99.8% or less of the inner diameter d2 of the outer can 20.
- a central hole 29 is formed in the center of the upper insulating plate 26.
- the central hole 29 is a substantially rectangular shape in which each corner is rounded in an arc shape, but may be circular, oval, or other polygon.
- the maximum width of the central hole 29 is preferably smaller than the width W (FIG. 9) of the positive electrode lead 16 so that the positive electrode lead 16 does not cause a short circuit due to contact with the electrode group 14 through the central hole 29.
- a columnar space (not shown) along the winding axis direction ⁇ is formed inside the innermost peripheral surface which is the central portion including the winding axis ⁇ of the electrode group 14. It is preferable that the central hole 29 faces the columnar space when viewed from the central axis O direction of the secondary battery 10 and does not face the electrode group 14. In this case, even if the exposed portion of the positive electrode lead 16 from the insulating tape is present directly above the center hole 29, the positive electrode lead 16 does not come into contact with the electrode group 14 through the center hole 29, and the electrode group 14 and the positive electrode are positive. A short circuit with the lead 16 can be effectively prevented.
- a substantially semicircular arc-shaped lead hole 27 is formed in one half of the upper insulating plate 26 (lower half of FIG. 5A) so as to avoid the central hole 29.
- the center hole 29 and the lead hole 27 are preferably enlarged, respectively, from the viewpoint of improving exhaust performance when gas is generated inside the secondary battery 10.
- the outer edge portion of the lead hole 27 is defined with reference to an arc concentric with the outer peripheral circle 26a of the upper insulating plate 26 and a string connecting both ends thereof.
- the outer edge portion of the lead hole 27 includes an outer curved portion 27a, an inner curved portion 27b, and straight portions 28a and 28b.
- the outer curved portion 27a is arranged along the reference arc, and the straight portions 28a and 28b are arranged along the strings connecting both ends of the reference arc.
- the outer curved portion 27a may coincide with the reference arc. In this case, the straight portions 28a and 28b are directly connected to both ends of the outer curved portion 27a.
- the reference arc is preferably an inferior arc smaller than a semicircle.
- the inner curved portion 27b is arranged so as to avoid the central hole 29.
- the inner curved portion 27b is also preferably arranged along an arc concentric with the outer peripheral circle 26a of the upper insulating plate 26.
- the inner curved portion 27b can be omitted depending on the positional relationship between the lead hole 27 and the center hole 29. In this case, the straight lines 28a and 28b form one straight line.
- the reference is drawn by drawing an extension line La along the reference arc from the first end P1 of the outer curved portion 27a.
- the arc that becomes can be specified.
- the R portion 30 serving as the connecting portion between the outer curved portion 27a and the straight portion 28a has a shape in which the connecting portion between the reference arc and the chord is chamfered.
- the R portion 31 interposed between the straight portions 28a and 28b and the inner curved portion 27b is the same applies to the R portion 31 interposed between the straight portions 28a and 28b and the inner curved portion 27b.
- the aperture ratio is not particularly limited, but is preferably 11% or more. If the aperture ratio is less than 11%, the exhaust path when gas is generated on the electrode group 14 side of the secondary battery 10 becomes small, and the exhaust performance becomes insufficient.
- the upper limit of the aperture ratio can be appropriately determined according to the strength of the upper insulating plate 26, but for example, it can be 60% or less, preferably 40% or less, and more preferably 20% or less. ..
- the thickness of the upper insulating plate 26 is, for example, 0.2 mm or more and 0.5 mm or less. If this thickness is less than 0.2 mm, the strength of the upper insulating plate 26 is lowered, and when an impact is applied to the secondary battery 10, the electrode group 14 may pop out toward the sealing body 22 side. If the thickness of the upper insulating plate 26 is larger than 0.5 mm, the internal volume of the battery becomes small, so that the capacity of the battery is significantly reduced.
- FIG. 6 shows the positive electrode lead 16 and the lead hole 46 when the upper insulating plate 45 is viewed from above when the positive electrode lead 16 is led out from the circumferential center position of the lead hole 46 in the secondary battery of the comparative example. It is a figure which shows the positional relationship with.
- FIG. 7 is a diagram corresponding to FIG. 6 in the case where the positive electrode lead 16 is led out from one end in the circumferential direction of the lead hole 46 in the secondary battery of the comparative example.
- the upper insulating plate 45 of the comparative example shown in FIG. 6 has the same planar shape as the upper insulating plate described in Patent Document 1. Specifically, the upper insulating plate 45 has a central hole 29 formed in the central portion and a substantially semicircular arc-shaped lead hole 46 formed in one side half portion (lower half portion in FIG. 6). And the outer peripheral holes 48 formed at a plurality of positions in the circumferential direction of the other side half portion (upper half portion in FIG. 6). As for the outer edge portion of the lead hole 46, the outer curved portion 46a is also arranged along an arc concentric with the outer peripheral circle 45a of the upper insulating plate 45.
- the straight lines 47a and 47b interposed between the outer curved portion 46a and the inner curved portion 46b connect both ends of the reference arc to the center of the arc, not in the chord direction. They are arranged along the radial direction.
- the positive electrode lead 16 penetrating the lead hole 46 is bent toward the central axis O of the secondary battery, as shown by the positive electrode lead 16 of the alternate long and short dash line in FIG.
- the shaded portion of the positive electrode lead 16 indicates a portion to which the insulating tape is attached, and the plain portion indicates an exposed portion of the conductive portion from the insulating tape.
- the positive electrode lead 16 when assembling the secondary battery, has a lead hole as shown in FIG. 7, depending on the relationship between the lead position of the positive electrode lead 16 from the electrode group and the circumferential position of the upper insulating plate 45. There is a possibility that it is derived upward from one end in the circumferential direction of 46 (the left end in FIG. 7). In this case, if the positive electrode lead 16 of the alternate long and short dash line in FIG. 7 is bent toward the central axis O of the secondary battery, the exposed portion of the positive electrode lead 16 faces the electrode group through the lead hole 46. There is no. On the other hand, as shown by the solid positive electrode lead 16 in FIG.
- FIG. 8 is a diagram showing a difference between the shape of the lead hole 27 of the upper insulating plate 26 of the embodiment and the shape of the lead hole 46 of the comparative example.
- the straight lines 47a and 47b are arranged along the radial direction connecting both ends of the reference arc to the center of the arc, whereas the implementation shown in FIG. 8 (b).
- the straight lines 28a and 28b are arranged along the strings connecting both ends of the reference arc. Due to this difference, in the embodiment, the ratio of the length of the inner curved portion 27b to the length of the outer curved portion 27a can be made smaller than that of the comparative example.
- the positive electrode lead led out from one end of the lead hole 27 (for example, the left end of FIG. 8B) is the other end of the lead hole 27. (For example, the right end portion in FIG. 8B) becomes difficult to face.
- FIG. 9 is a diagram corresponding to FIG. 7 in the embodiment.
- the straight portions 28a and 28b connecting the outer curved portion 27a and the inner curved portion 27b of the lead hole 27 are the reference of the outer curved portion 27a. It is arranged along the string connecting both ends of the arc.
- the positive electrode lead 16 led out from one end in the circumferential direction of the lead hole 27 (the left end in FIG. 9) is displaced from the central axis O of the secondary battery.
- the upper insulating plate 26 since the upper insulating plate 26 has only the lead hole 27 and the central hole 29 as through holes, it is possible to more effectively prevent the electrode group 14 and the positive electrode lead 16 from being short-circuited through the through holes. ..
- the non-opposing portion 12a that does not face the positive electrode 11 via the separator 13 is wound 1.25 turns or more from the inner end in the winding direction of the electrode group 14.
- the negative electrode mixture layer forming portion 12c on which the negative electrode mixture layer 12f is formed is wound around 0.75 turns or more.
- the positive electrode 11 does not face any of both sides of the negative electrode mixture layer forming portion 12c.
- the negative electrode mixture layer forming portion 12c does not react with the positive electrode 11, so that the portion near the inner end in the winding direction including the negative electrode core portion of the negative electrode mixture layer forming portion 12c is an electrode.
- the negative electrode mixture layer forming portion 12c has higher strength than the portion where only the negative electrode core body is exposed on both sides. Therefore, the portion remaining in the tubular shape serves as an exhaust passage, and the high-temperature and high-pressure gas generated inside the battery at the time of ignition can be guided in the vertical direction and efficiently exhausted. Therefore, bursting of the secondary battery 10 due to an excessive increase in the internal pressure of the secondary battery 10 can be suppressed. Further, since it is not necessary to provide the metal tubular member in the winding core portion of the secondary battery 10 in order to efficiently exhaust the gas in this way, the cost increase can be suppressed. As a result, it is possible to realize a structure capable of securing an exhaust passage of the winding core portion of the electrode group 14 when the secondary battery 10 ignites at low cost.
- NMP was removed at a temperature of 100 to 150 ° C. in a heated dryer, rolled by a roll press to form a positive electrode mixture layer, and the positive electrode after rolling was heated to 200 ° C.
- the heat treatment was performed by contacting the rollers for 5 seconds.
- a long positive electrode core body on which the positive electrode mixture layer was formed was cut into an electrode size of a predetermined size to prepare a positive electrode 11, and then an aluminum positive electrode lead 16 was attached on the positive electrode core body.
- the thickness of the positive electrode 11 after production is 0.144 mm, the width is 62.6 mm, and the length is 861 mm.
- the negative electrode active material a mixture of 95 parts by weight of graphite powder and 5 parts by weight of silicon oxide was used. Then, 1 part by weight of this mixture, carboxymethyl cellulose (CMC) as a thickener, and 1 part by weight of a dispersion of styrene-butadiene rubber as a binder are dispersed in water to combine the negative electrodes. The agent slurry was prepared. This negative electrode mixture slurry was applied to both sides of a negative electrode core made of copper foil having a thickness of 8 ⁇ m to form a negative electrode coated portion. At this time, the outermost peripheral surface of the electrode group was formed to be the negative electrode core body.
- CMC carboxymethyl cellulose
- the thickness of the negative electrode mixture layer was adjusted by compressing with a compression roller so that the negative electrode thickness became 160 ⁇ m. Then, a long negative electrode core body on which the negative electrode mixture layer is formed is cut into an electrode size of a predetermined size to prepare a negative electrode 12 having negative electrode mixture layers formed on both sides, and then on the negative electrode core body. A nickel-copper-nickel negative electrode lead 40 was attached. The width of the negative electrode 12 after production is 64.2 mm, and the length is 959 mm.
- the electrode group 14 was formed by winding it in a cylindrical shape between the positive electrode 11 and the negative electrode 12 via a polyethylene separator 13.
- Ethylene carbonate (EC) and dimethylmethyl carbonate (DMC) are mixed at a volume ratio of 1: 3, and 5 parts by weight of vinylene carbonate (VC) is added to 100 parts by weight of the mixed solvent, and the mixed solvent is added.
- VC vinylene carbonate
- LiPF 6 was dissolved in LiPF 6 to a concentration of 1.5 mol / L to prepare a non-aqueous electrolytic solution.
- the upper insulating plate 26 As the upper insulating plate 26, a circular plate material having a thickness of 0.3 mm made of polypropylene resin was used, and as shown in FIG. 5A, a lead hole 27 and a center hole 29 through which the positive electrode lead 16 penetrated were formed.
- the central hole 29 has a length of 2.2 mm and a width of 3 mm. Then, the lead hole 27 through which the positive electrode lead 16 penetrates was formed so that the total aperture ratio of the central hole 29 and the lead hole 27 was 18.3%.
- the upper insulating plate 26 and the lower insulating plate were arranged above and below the electrode group 14, and the electrode group 14 was housed in the outer can 20.
- the positive electrode lead 16 was led out from the electrode group 14 through the lead hole 27 of the upper insulating plate 26.
- the negative electrode lead 40 was welded to the outer can 20 of the battery case 18, and the positive electrode lead 16 was welded to the sealing body 22 having an internal pressure actuated safety valve. Then, a non-aqueous electrolytic solution was injected into the battery case 18 by a reduced pressure method.
- the secondary battery 10 was manufactured by crimping the sealing body 22 to the upper open end of the outer can 20 via the gasket 24.
- the capacity of the secondary battery 10 was 4600 mAh.
- the non-opposing portion 12a that does not face the positive electrode 11 via the separator 13 was wound 1.75 times. Further, among the non-opposing portions 12a, the negative electrode mixture layer forming portion 12c on which the negative electrode mixture layer 12f was formed was wound 0.75 turns, and the negative electrode core body exposed portion 12d was wound one turn.
- Experimental Example 2 is the same as Experimental Example 1 except that the lead hole 27 through which the positive electrode lead 16 penetrates is formed so that the total aperture ratio of the central hole 29 and the lead hole 27 is 15.4%. Such a secondary battery was manufactured.
- the shape of the upper insulating plate 26 of Experimental Example 2 is shown in the column of Experimental Example 2 of FIG. 11 described later.
- FIG. 10 is a diagram corresponding to FIG. 5 in the upper insulating plate 26 according to the secondary battery of Experimental Example 3.
- the lead hole 27 through which the positive electrode lead 16 (FIG. 1) penetrates is provided so that the total aperture ratio of the center hole 29 and the lead hole 27 is 11.7%.
- a secondary battery according to Experimental Example 3 was produced in the same manner as in Experimental Example 1 except that it was formed.
- the shape of the upper insulating plate 26 of Experimental Example 3 is also shown in the column of Experimental Example 3 of FIG. 11 described later.
- the lead hole 27 is significantly smaller than in the cases of Experimental Examples 1 and 2, the lead hole 27 is not formed with an inner curved portion for avoiding the central hole 29.
- the outer edge portion of the lead hole 27 is an outer curved portion 27a arranged along an arc concentric with the outer peripheral circle 26a of the upper insulating plate 26 in a plan view, and R portions 30 at both ends of the outer curved portion 27a.
- the straight line portion 28c is arranged along the string connecting both ends of the reference arc.
- Experimental Example 4 is the same as Experimental Example 1 except that the lead hole 27 through which the positive electrode lead 16 penetrates is formed so that the total aperture ratio of the central hole 29 and the lead hole 27 is 5.6%. Such a secondary battery was manufactured.
- the shape of the upper insulating plate 26 of Experimental Example 4 is shown in the column of Experimental Example 4 of FIG. 11 described later.
- the lead hole 27 of Experimental Example 4 also does not have an inner curved portion formed like the lead hole 27 of Experimental Example 3.
- FIG. 11 is a diagram comparing the shape of the upper insulating plate 26, the aperture ratio with respect to the area of the outer peripheral circle of the upper insulating plate 26, and the burst rate of the battery case in the secondary batteries according to Experimental Examples 1 to 4. ..
- the battery case in the overheating test Burst rate was reduced to 0.
- the aperture ratio was less than 11%, the battery case burst due to the overheating test.
- FIG. 12 is a diagram corresponding to FIG. 1 in another example of the embodiment.
- FIG. 13 is a diagram corresponding to FIG. 7 in another example of the embodiment.
- outer peripheral holes 32 as a plurality of (four in FIG. 13) through holes are formed side by side in the circumferential direction in the half portion of the upper insulating plate 26 opposite to the lead hole 27.
- the distance from the central axis O of the secondary battery 10a to the second curved portion 16b of the positive electrode lead 16 (the distance to the portion of the second curved portion 16b farthest from the central axis O) is set to L1, and the secondary battery is used.
- the maximum width of the other through hole is set to the width W of the positive electrode lead 16. If it is made smaller than (FIG. 9), the distance L2 from the central axis O of the secondary battery 10 to the other through holes is set from the central axis O of the secondary battery 10 to the second curved portion 16b of the positive electrode lead 16. The distance may be less than L1.
- 10,10a Cylindrical non-aqueous electrolyte secondary battery (secondary battery), 11 positive electrode, 12 negative electrode, 12a non-opposing part, 12b facing part, 12c negative electrode mixture layer forming part, 12d negative electrode core body exposed part, 12f negative electrode combination Agent layer, 13 separator, 14 electrode group, 16 positive electrode lead, 16a 1st curved part, 16b 2nd curved part, 18 battery case, 20 outer can, 21 overhanging part, 22 sealing body, 24 gasket, 26 upper insulating plate, 26a outer circle, 27 lead hole, 27a outer curved part, 27b inner curved part, 28a, 28b, 28c straight part, 29 center hole, 30, 31 R part, 32 outer peripheral hole, 40 negative electrode lead, 45 upper insulating plate, 46 Lead hole, 48 outer peripheral hole.
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Abstract
Description
図1は、実施形態の円筒形非水電解質二次電池10の模式的な断面図である。図2は、図1のA-A断面の電極群14における巻き方向内端寄り部分を模式的に示す図である。図1、図2に示すように、円筒形非水電解質二次電池10は、巻回型の電極群14と、非水電解質(図示せず)とを備える。図2に示すように、電極群14は、正極11と、負極12と、セパレータ13とを有し、正極11と負極12がセパレータ13を介して渦巻状に巻回されてなる。図2では配置関係を分かりやすくするために、負極12を実線で示し、正極11を破線で示し、セパレータ13を一点鎖線で示している。図2では、正極11、負極12、セパレータ13の隙間を誇張して示している。図1では、電極群14として、外周側から見た形状を示している。以下では、電極群14の巻き軸方向一方側を「上」、巻き軸方向他方側を「下」という場合がある。非水電解質は、非水溶媒と、非水溶媒に溶解した電解質塩とを含む。非水電解質は、液体電解質に限定されず、ゲル状ポリマー等を用いた固体電解質であってもよい。以下では、円筒形非水電解質二次電池10は、二次電池10と記載する。
本開示の発明者は、次のように実験例1~4の二次電池10を作製し、高温過熱試験を行った。
[正極の作製]
正極活物質として、LiNi0.88Co0.09Al0.03O2で表されるアルミニウム含有ニッケルコバルト酸リチウムを用いた。その後、100重量部のLiNi0.88Co0.09Al0.03O2と、1.0重量部のアセチレンブラックと、0.9重量部のポリフッ化ビニリデン(PVDF)(結着剤)とを、適量のN-メチル-2-ピロリドン(NMP)の溶剤中で混合して、正極合剤スラリーを得た。このペースト状の正極合剤スラリーを厚み15μmのアルミニウム箔からなる長尺な正極芯体の両面に均一に塗布した。次に、加熱した乾燥機中で、100~150℃の温度でNMPを除去後、ロールプレス機により圧延して正極合剤層を形成し、さらに圧延加工後の正極を、200℃に熱したローラーに5秒間接触させることで熱処理を行った。そして、正極合剤層が形成された長尺な正極芯体を所定サイズの電極サイズに切断して正極11を作製し、その後、正極芯体上にアルミニウム製の正極リード16を取り付けた。作製後の正極11の厚みは0.144mm、幅は62.6mm、長さは861mmである。
負極活物質として、黒鉛粉末を95重量部と、酸化ケイ素を5重量部との比率で混合したものを用いた。その後、この混合したものと、増粘剤としてのカルボキシメチルセルロース(CMC)を1重量部、及び結着剤としてのスチレン-ブタジエンゴムのディスパージョンを1重量部とを水に分散させて、負極合剤スラリーを調整した。この負極合剤スラリーを、厚さ8μmの銅箔からなる負極芯体の両面に塗布して負極塗工部を形成した。このとき、電極群の最外周面が負極芯体となるように形成した。次いで、加熱した乾燥器中で塗膜を乾燥させた後、負極厚みが160μmになるように圧縮ローラーで圧縮し負極合剤層の厚みを調整した。そして、負極合剤層が形成された長尺な負極芯体を所定サイズの電極サイズに切断して、両面に負極合剤層が形成された負極12を作製し、その後、負極芯体上にニッケル-銅-ニッケル製の負極リード40を取り付けた。作製後の負極12の幅は64.2mm、長さは959mmである。
正極11と負極12との間にポリエチレン製のセパレータ13を介して円筒状に巻回し、電極群14を構成した。
エチレンカーボネート(EC)と、ジメチルメチルカーボネート(DMC)とを、1:3の体積比で混合し、その混合溶媒の100重量部に、ビニレンカーボネート(VC)を5重量部添加し、当該混合溶媒に1.5モル/Lの濃度になるようにLiPF6を溶解させて、非水電解液を調製した。
上部絶縁板26にはポリプロピレン樹脂から構成される厚みが0.3mmの円形状の板材を用い、図5Aに示したように、正極リード16が貫通するリード孔27及び中心孔29を形成した。中心孔29は、縦2.2mm、横3mmである。そして、中心孔29とリード孔27との合計の開口率が18.3%となるように、正極リード16が貫通するリード孔27を形成した。
上記の電極群14の上と下とに上部絶縁板26、下部絶縁板をそれぞれ配置し、電極群14を外装缶20に収納した。正極リード16は上部絶縁板26のリード孔27を通して電極群14から導出した。負極リード40を電池ケース18の外装缶20に溶接し、正極リード16を内圧作動型の安全弁を有する封口体22に溶接した。その後、電池ケース18の内部に非水電解液を減圧方式により注入した。最後に、封口体22を、ガスケット24を介して外装缶20の上部の開口端部に加締めることにより二次電池10を作製した。二次電池10の容量は4600mAhであった。また、負極12において、正極11にセパレータ13を介して対向しない非対向部12aは、1.75周巻回した。また、非対向部12aのうち、負極合剤層12fが形成された負極合剤層形成部12cは、0.75周巻回し、負極芯体露出部12dは、1周分巻回した。
中心孔29とリード孔27との合計の開口率が15.4%となるように、正極リード16が貫通するリード孔27を形成したこと以外は、実験例1と同様にして実験例2に係る二次電池を作製した。実験例2の上部絶縁板26の形状は、後述の図11の実験例2の欄に示している。
図10は、実験例3の二次電池に係る上部絶縁板26における図5に対応する図である。図10に示すように、上部絶縁板26において、中心孔29とリード孔27との合計の開口率が11.7%となるように、正極リード16(図1)が貫通するリード孔27を形成したこと以外は、実験例1と同様にして実験例3に係る二次電池を作製した。後述の図11の実験例3の欄にも、実験例3の上部絶縁板26の形状を示している。図10に示すように、リード孔27が実験例1,2の場合より大幅に小さくなったので、リード孔27には中心孔29を避けるための内側曲線部が形成されていない。具体的には、リード孔27の外縁部は、平面視で上部絶縁板26の外周円26aと同心の円弧に沿って配置された外側曲線部27aと、外側曲線部27aの両端にR部30を介して接続された直線部28cとを含む。直線部28cは、基準の円弧の両端を結ぶ弦に沿って配置されている。
中心孔29とリード孔27との合計の開口率が5.6%となるように、正極リード16が貫通するリード孔27を形成したこと以外は、実験例1と同様にして実験例4に係る二次電池を作製した。後述の図11の実験例4の欄に、実験例4の上部絶縁板26の形状を示している。実験例4のリード孔27も、実験例3のリード孔27と同様に内側曲線部が形成されていない。
実験例1~4のそれぞれ10個の二次電池を1380mAの定電流で電圧が4.2Vになるまで充電し、次いで4.2Vの定電圧で電流が92mAになるまで充電した。そのように充電された二次電池を用いて、排気性を評価するための過熱試験を実施した。過熱試験は、電池モジュールの類焼環境を模擬する試験として、300℃の加熱炉の中で輻射熱により実験例1~4のそれぞれ10個の二次電池を過熱し、強制的に熱暴走させて電池ケースの破裂率を検証した。
図11は、実験例1~4に係る二次電池において、上部絶縁板26の形状と、上部絶縁板26の外周円の面積に対する開口率と、電池ケースの破裂率とを比較した図である。図11に示すように、上部絶縁板26の外周円の面積に対するリード孔27及び中心孔29の合計の開口率が11%以上である実験例1~3によれば、過熱試験での電池ケースの破裂率を0にできた。一方、この開口率が11%未満である実験例4では、過熱試験により電池ケースの破裂が生じた。これにより、開口率を11%以上とすることによって、電池の内部で発生するガスを迅速に排出できる、より安全性の高い二次電池を実現できることを確認できた。
図12は、実施形態の別例において、図1に対応する図である。図13は、実施形態の別例において、図7に対応する図である。本例の二次電池10aでは、上部絶縁板26のリード孔27とは反対側の半部において、複数(図13では4つ)の貫通孔としての外周孔32が周方向に並んで形成される。さらに、二次電池10aの中心軸Oから正極リード16の第2湾曲部16bまでの距離(第2湾曲部16bのうち中心軸Oから最も離間した部分までの距離)をL1とし、二次電池10の中心軸Oから外周孔32までの距離(外周孔32のうち中心軸Oに最も近接した部分までの距離)をL2とした場合に、L1及びL2がL2>L1を満たすように規制される。これにより、上部絶縁板26にリード孔27及び中心孔29以外に、他の貫通孔としての外周孔32が形成される場合でも、正極リード16の露出部分が外周孔32を通じて電極群14に接触して短絡することを防止できる。また、上部絶縁板26の貫通孔を多くできることにより、内部ガスの排出性を高くできる。このように本開示の構成は、上部絶縁板26にリード孔27及び中心孔29以外の貫通孔を形成することもできる。本例において、その他の構成及び作用は、図1~5、図9の構成と同様である。
Claims (7)
- 外装缶、前記外装缶の一端を塞ぐ封口体、前記外装缶の内部に配置された電極群、及び前記封口体と前記電極群の間に配置された絶縁板を備える円筒形非水電解質二次電池であって、
前記電極群は、正極と負極とがセパレータを介して渦巻き状に巻回され、
前記絶縁板は、前記電極群から導出する正極リードが貫通するリード孔、及び中心部を貫通する中心孔を有する円板状であり、
前記リード孔の外縁部は、平面視で、前記絶縁板の外周円と同心の円弧に沿って配置された曲線部と、前記円弧の両端を結ぶ弦に沿って配置された直線部とを含む、
円筒形非水電解質二次電池。 - 請求項1に記載の円筒形非水電解質二次電池において、
前記曲線部と前記直線部の接続部は、平面視で前記円弧と前記弦の接続部が面取りされた形状を有する、
円筒形非水電解質二次電池。 - 請求項1又は請求項2に記載の円筒形非水電解質二次電池において、
前記絶縁板は、貫通孔として前記リード孔及び前記中心孔のみを有する、
円筒形非水電解質二次電池。 - 請求項3に記載の円筒形非水電解質二次電池において、
前記封口体は、内圧が所定の圧力に達したときに、内部の発生ガスを開放するように構成され、
前記中心孔を前記電極群の巻き軸方向から見た場合に、前記中心孔が前記電極群と対向せず、前記リード孔及び前記中心孔の合計の開口率が前記絶縁板の外周円内の面積に対し、11%以上である、
円筒形非水電解質二次電池。 - 請求項1から請求項4のいずれか1項に記載の円筒形非水電解質二次電池において、
前記絶縁板の材料はポリオレフィン系樹脂である、
円筒形非水電解質二次電池。 - 請求項1から請求項5のいずれか1項に記載の円筒形非水電解質二次電池において、
前記絶縁板の厚みは0.2mm以上、0.5mm以下である、
円筒形非水電解質二次電池。 - 請求項1から請求項6のいずれか1項に記載の円筒形非水電解質二次電池において、
前記負極は、
前記電極群の巻き方向内端から前記セパレータを介して前記正極に対向しない状態で1.25周以上巻回された非対向部を含み、
前記非対向部は、少なくとも一方の面に巻き方向外端から巻き方向内側に連続して、負極合剤層が形成された負極合剤層形成部を有し、
前記負極合剤層形成部は、0.75周以上巻回される、
円筒形非水電解質二次電池。
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| EP20832370.9A EP3993131A4 (en) | 2019-06-28 | 2020-06-24 | CYLINDRICAL SECONDARY CELL WITH ANHYDROUS ELECTROLYTE |
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| WO2024111413A1 (ja) * | 2022-11-25 | 2024-05-30 | パナソニックエナジー株式会社 | 円筒形の非水電解質二次電池 |
| WO2024111410A1 (ja) * | 2022-11-25 | 2024-05-30 | パナソニックエナジー株式会社 | 円筒形の非水電解質二次電池 |
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| EP3993131A1 (en) | 2022-05-04 |
| CN114026725A (zh) | 2022-02-08 |
| CN114026725B (zh) | 2024-12-13 |
| US20220416380A1 (en) | 2022-12-29 |
| JPWO2020262437A1 (ja) | 2020-12-30 |
| US12381297B2 (en) | 2025-08-05 |
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| EP3993131A4 (en) | 2022-08-17 |
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