WO2014118965A1 - 蓄電素子 - Google Patents
蓄電素子 Download PDFInfo
- Publication number
- WO2014118965A1 WO2014118965A1 PCT/JP2013/052334 JP2013052334W WO2014118965A1 WO 2014118965 A1 WO2014118965 A1 WO 2014118965A1 JP 2013052334 W JP2013052334 W JP 2013052334W WO 2014118965 A1 WO2014118965 A1 WO 2014118965A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- current collector
- insertion portion
- external terminal
- lid
- bus bar
- Prior art date
Links
- 238000003860 storage Methods 0.000 title claims abstract description 17
- 230000005611 electricity Effects 0.000 title claims abstract description 7
- 238000003780 insertion Methods 0.000 claims abstract description 89
- 230000037431 insertion Effects 0.000 claims abstract description 89
- 238000003466 welding Methods 0.000 claims abstract description 27
- 238000010248 power generation Methods 0.000 claims abstract description 13
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 239000012212 insulator Substances 0.000 description 30
- 239000011888 foil Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 238000002788 crimping Methods 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- 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
- H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
- H01M50/514—Methods for interconnecting adjacent batteries or cells
- H01M50/516—Methods for interconnecting adjacent batteries or cells by welding, soldering or brazing
-
- 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
- H01M50/176—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for prismatic or rectangular cells
-
- 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
-
- 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
- H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
- H01M50/505—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing comprising a single busbar
-
- 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
- H01M50/543—Terminals
- H01M50/564—Terminals characterised by their manufacturing process
- H01M50/566—Terminals characterised by their manufacturing process by welding, soldering or brazing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
- H01M50/543—Terminals
- H01M50/547—Terminals characterised by the disposition of the terminals on the cells
- H01M50/55—Terminals characterised by the disposition of the terminals on the cells on the same side of the cell
-
- 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
- H01M50/543—Terminals
- H01M50/552—Terminals characterised by their shape
- H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
-
- 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
- H01M50/543—Terminals
- H01M50/562—Terminals characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a power storage element.
- a positive electrode coated with a positive electrode active material on a positive electrode foil, a negative electrode coated with a negative electrode active material on a negative electrode foil, and a separator for insulating each of them are rolled up.
- a flat wound electrode group is formed as a power generation element.
- the wound electrode group is electrically connected to a positive electrode external terminal and a negative electrode external terminal provided on the battery lid of the battery container.
- the wound electrode group is accommodated in a battery can of the battery container, and the opening of the battery can is sealed and welded with a battery lid.
- a prismatic secondary battery is formed by injecting an electrolytic solution from a liquid injection hole of a battery container containing a wound electrode group, inserting a liquid injection stopper, and sealing welding by laser welding.
- a battery assembly is formed by electrically connecting positive electrode external terminals and negative electrode external terminals of a plurality of rectangular secondary batteries with a conductive member such as a bus bar.
- the bus bar is connected to the prismatic secondary battery by being screwed to the external terminal by bolts and nuts or by being welded to the external terminal.
- Patent Document 1 discloses a secondary battery that can connect a bus bar to an external terminal by welding.
- the secondary battery described in Patent Document 1 is a connection member (electrical current collecting member in Patent Document 1) joined to a power generation element and a connection member that electrically connects an external terminal arranged on the battery lid ( Caulking member).
- connection member electric current collecting member in Patent Document 1
- connection member that electrically connects an external terminal arranged on the battery lid ( Caulking member).
- Caulking member an external terminal arranged on the battery lid
- a member that electrically connects the bus bar and the power generation element is configured by an external terminal, a connection member, and a current collector, and is connected to each of the external terminal and the current collector. Since the members are connected, the manufacturing process may be complicated. Further, in the secondary battery described in Patent Document 1, since two connection portions are provided in the conduction path between the external terminal and the current collector, the contact resistance may be increased.
- the external terminal of the secondary battery described in Patent Document 1 includes a caulking fixing portion to which the connecting member is caulked and a bus bar joining portion to which the bus bar is joined.
- the external terminal has a downward slope from the bus bar joint portion toward the caulking fixing portion, and the caulking fixing portion and the bus bar joining portion are arranged at different levels. For this reason, it is difficult to perform the caulking process between the current collector and the connecting member by bringing the jig into contact with the caulking fixing portion which is a part of the external terminal, and improvement in workability has been desired.
- an electricity storage element includes a power generation element having an electrode, a can that houses the power generation element, a lid that seals an opening of the can, an external terminal that is disposed on the lid, and a power generation element
- a current collector for connecting the electrode and the external terminal, and the external terminal includes a bus bar welded portion having a bus bar weld surface to which the bus bar is welded, and a current collector connecting portion having a caulking jig contact surface.
- the current collector connection part is inserted through the through-hole of the lid, and the insertion part is fixed by caulking the tip to the current collector.
- the bus bar welded part and the current collector connection part are integrally arranged on the lid.
- the jig contact surface extends from the bus bar weld surface in the same plane as the bus bar weld surface.
- the contact resistance can be reduced, the number of assembling steps for the rectangular secondary battery can be reduced, and the yield can be improved. be able to. Furthermore, since the jig contact surface extends from the bus bar weld surface in the same plane as the bus bar weld surface, the workability of the caulking process can be improved.
- FIG. 1 is an external perspective view of a prismatic secondary battery as an embodiment of a power storage element of the present invention.
- the disassembled perspective view which shows the structure of a square secondary battery.
- the perspective view which shows the winding electrode group.
- the disassembled perspective view which shows a cover assembly.
- Sectional drawing which shows the structure of a lid
- (A) is an external perspective view of the external terminal
- (b) is a plan view of the external terminal viewed from the direction D of (a)
- (c) is a cross-sectional view of the external terminal cut along line CC of (b). .
- the figure which shows the process of crimping the front-end
- FIG. 1 is an external perspective view of a prismatic secondary battery 100 as an embodiment of a power storage element
- FIG. 2 is an exploded perspective view showing the configuration of the prismatic secondary battery 100.
- the square secondary battery 100 includes a battery container including a battery can 101 and a battery lid 102.
- the material of the battery can 101 and the battery lid 102 is aluminum or an aluminum alloy.
- the battery can 101 is formed in a flat rectangular box shape with one end opened by performing deep drawing.
- the battery can 101 includes a rectangular plate-like bottom plate 101c, a pair of wide side plates 101a rising from each of a pair of long sides of the bottom plate 101c, and a pair of narrow side plates 101b rising from each of a pair of short sides of the bottom plate 101c. And have.
- the battery can 101 accommodates a wound electrode group 170 (see FIG. 3) held by the lid assembly 107 (see FIG. 4).
- Positive electrode current collector 180 joined to positive electrode 174 (see FIG. 3) of wound electrode group 170, negative electrode current collector 190 joined to negative electrode 175 (see FIG. 3) of wound electrode group 170, and wound.
- the electrode group 170 is accommodated in the battery can 101 while being covered with the insulating case 108.
- the material of the insulating case 108 is an insulating resin such as polypropylene, and the battery can 101 and the wound electrode group 170 are electrically insulated.
- the battery lid 102 has a rectangular flat plate shape and is laser-welded so as to close the opening of the battery can 101. That is, the battery lid 102 seals the opening of the battery can 101.
- a positive electrode external terminal 104 and a negative electrode external terminal 105 electrically connected to the positive electrode 174 and the negative electrode 175 (see FIG. 3) of the wound electrode group 170 are disposed on the battery lid 102. ing.
- the positive external terminal 104 is electrically connected to the positive electrode 174 (see FIG. 3) of the wound electrode group 170 via the positive current collector 180, and the negative external terminal 105 is connected to the negative current collector.
- the electrode is electrically connected to the negative electrode 175 (see FIG. 3) of the wound electrode group 170 via 190. Therefore, electric power is supplied to the external device via the positive external terminal 104 and the negative external terminal 105, or external generated power is supplied to the wound electrode group 170 via the positive external terminal 104 and the negative external terminal 105. Charged.
- the battery lid 102 is provided with a liquid injection hole 106a for injecting an electrolytic solution into the battery container.
- the liquid injection hole 106a is sealed by a liquid injection plug 106b after the electrolytic solution is injected.
- the electrolytic solution for example, a non-aqueous electrolytic solution in which a lithium salt such as lithium hexafluorophosphate (LiPF 6 ) is dissolved in a carbonate-based organic solvent such as ethylene carbonate can be used.
- the battery cover 102 is provided with a gas discharge valve 103.
- the gas discharge valve 103 is formed by partially thinning the battery lid 102 by press working.
- the thin-walled member may be attached to the opening of the battery lid 102 by laser welding or the like, and the thin portion may be used as a gas discharge valve.
- the gas discharge valve 103 is heated when the square secondary battery 100 generates heat due to an abnormality such as overcharge, and when the pressure in the battery container rises and reaches a predetermined pressure, the gas discharge valve 103 is opened and gas is discharged from the inside. By discharging, the pressure in the battery container is reduced.
- FIG. 3 is a perspective view showing the wound electrode group 170 and shows a state where the winding end side of the wound electrode group 170 is developed.
- the wound electrode group 170 which is a power generation element, has a laminated structure by winding a long positive electrode 174 and a negative electrode 175 in a flat shape around the wound central axis W with separators 173a and 173b interposed therebetween. ing.
- the positive electrode 174 has a positive electrode active material mixture layer 176 formed on both surfaces of the positive foil 171.
- the positive electrode active material mixture is a mixture of a positive electrode active material and a binder.
- the negative electrode 175 is formed by forming layers 177 of a negative electrode active material mixture on both surfaces of a negative electrode foil 172.
- the negative electrode active material mixture is a mixture of a negative electrode active material and a binder.
- the positive foil 171 is an aluminum foil having a thickness of about 20 to 30 ⁇ m
- the negative foil 172 is a copper foil having a thickness of about 15 to 20 ⁇ m.
- the material of the separators 173a and 173b is a microporous polyethylene resin through which lithium ions can pass.
- the positive electrode active material is a lithium-containing transition metal double oxide such as lithium manganate
- the negative electrode active material is a carbon material such as graphite capable of reversibly occluding and releasing lithium ions.
- One of the end portions of the winding electrode group 170 in the width direction, that is, the direction of the winding central axis W perpendicular to the winding direction is a laminated portion of the positive electrode 174 and the other is a laminated portion of the negative electrode 175. Yes.
- the laminated portion of the positive electrode 174 provided at one end is obtained by laminating the positive electrode uncoated portion where the positive electrode active material mixture layer 176 is not formed, that is, the exposed portion of the positive foil 171.
- the laminated portion of the negative electrode 175 provided at the other end is obtained by laminating an uncoated negative electrode portion where the negative electrode active material mixture layer 177 is not formed, that is, an exposed portion of the negative foil 172.
- the laminated portion of the positive electrode uncoated portion and the laminated portion of the negative electrode uncoated portion are respectively crushed in advance, and are respectively formed on the positive electrode current collector 180 and the negative electrode current collector 190 of the lid assembly 107 (see FIG. 4) described later.
- the electrodes are assembled by ultrasonic bonding to form an electrode assembly 109 (see FIG. 2).
- FIG. 5 is a cross-sectional view showing the configuration of the lid assembly 107.
- FIG. 5A is a sectional view taken along line BB in FIG.
- FIG. 5B is a cross-sectional view showing a state in which the constituent members of the lid assembly 107 are assembled, and shows a state before the tips of the positive electrode insertion portion 141b and the negative electrode insertion portion 151b are caulked.
- FIG. 5C is a cross-sectional view taken along the line AA in FIG. 1, and shows a state after the tips of the positive electrode insertion portion 141b and the negative electrode insertion portion 151b are caulked.
- FIG. 5 shows a configuration on the negative electrode side
- the positive electrode side has the same shape and configuration, and therefore, for convenience, reference numerals of components on the positive electrode side are given in parentheses.
- the lid assembly 107 includes a battery lid 102, a positive external terminal 104 provided at one end of the battery lid 102, and a negative electrode provided at the other end of the battery lid 102.
- the external terminal 105, a pair of external insulators 160, a pair of internal insulators 165, a pair of gaskets 169, a positive electrode current collector 180, and a negative electrode current collector 190 are configured.
- the material of the positive electrode external terminal 104 and the positive electrode current collector 180 is aluminum. As will be described later, the positive electrode external terminal 104 is electrically connected to the positive electrode current collector 180 by caulking the tip of the positive electrode insertion portion 141b to the seat surface portion 181 of the positive electrode current collector 180 (see FIG. 7).
- the material of the negative electrode external terminal 105 and the negative electrode current collector 190 is a copper alloy. As will be described later, the negative electrode external terminal 105 is electrically connected to the negative electrode current collector 190 by caulking the negative electrode insertion portion 151b to the seat surface portion 191 of the negative electrode current collector 190 (see FIG. 7).
- the positive external terminal 104 is attached to the battery lid 102 via an external insulator 160 and a gasket 169.
- the negative external terminal 105 is attached to the battery lid 102 via an external insulator 160 and a gasket 169.
- the positive electrode current collector 180 and the negative electrode current collector 190 are each attached to the battery lid 102 via an internal insulator 165.
- the material of the external insulator 160 and the internal insulator 165 is an insulating resin such as polypropylene (PP).
- the material of the gasket 169 is an insulating resin such as tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA).
- the prismatic secondary battery 100 is connected to another prismatic secondary battery (not shown) by a bus bar to constitute an assembled battery.
- bus bar 123 indicated by a two-dot chain line in FIG. 5C is connected to external terminals 104 and 105 of prismatic secondary battery 100 by laser welding.
- FIG. 6 is a component diagram of the external terminal
- FIG. 6 (a) is an external perspective view of the external terminal
- FIG. 6 (b) is a plan view of the external terminal viewed from the direction D of FIG. 6 (a)
- FIG. 6 (c) is a cross-sectional view of the external terminal cut along line CC in FIG. 6 (b).
- the positive external terminal 104 includes a bus bar welded portion 142 to which the bus bar 123 is electrically connected by laser welding, and a positive current collector 180 that is electrically connected by caulking.
- Current collector connection portion 141 that is connected electrically.
- the bus bar welded portion 142 and the current collector connecting portion 141 are integrally arranged on the battery lid 102.
- the negative electrode external terminal 105 includes a bus bar welded portion 152 to which the bus bar 123 is electrically connected by laser welding, and a current collector connection portion 151 to which the negative electrode current collector 190 is electrically connected by caulking.
- the bus bar welded portion 152 and the current collector connecting portion 151 are integrally arranged on the battery lid 102.
- the positive external terminal 104 and the negative external terminal 105 are each formed by forging or the like.
- the bus bar welded portion 142 of the positive external terminal 104 has a rectangular flat plate shape and is disposed on the outside of the battery container (see FIGS. 4 and 5). As shown in FIG. 6, the bus bar welded portion 142 has one surface as a lid-side contact surface 142f that contacts the terminal insulating portion 160a of the external insulator 160, and is opposite to the lid-side contact surface 142f. This surface is the welding surface 142s.
- the welding surface 142s is a flat surface parallel to the battery lid 102, and the bus bar 123 and the positive external terminal 104 are laser-welded with the bus bar 123 in contact with the welding surface 142s (see FIG. 5C).
- the bus bar welded portion 152 of the negative electrode external terminal 105 has a rectangular flat plate shape and is disposed on the outer side of the battery container (see FIGS. 4 and 5). As shown in FIG. 6, the bus bar welded portion 152 has one surface as a lid-side contact surface 152f that contacts the terminal insulating portion 160a of the external insulator 160, and is opposite to the lid-side contact surface 152f. This surface is a welding surface 152s.
- the welding surface 152s is a flat surface parallel to the battery cover 102, and the bus bar 123 and the negative electrode external terminal 105 are laser-welded with the bus bar 123 in contact with the welding surface 152s (see FIG. 5C).
- the current collector connecting portion 141 of the positive external terminal 104 includes a base portion 141a extending from the bus bar welded portion 142 along the battery lid 102, and a battery from the base portion 141a. It has a positive electrode insertion portion 141b protruding toward the inside of the container and a seal portion 141c provided on the outer periphery of the positive electrode insertion portion 141b.
- the base portion 141 a is formed so that the length in the direction orthogonal to the wide side plate 101 a gradually decreases as the length approaches the bus bar welded portion 142.
- the surface of the base portion 141a opposite to the battery lid 102 side is an upper die 20 of a jig used for caulking described later (see FIG. 7).
- the jig contact surface 141s is pressed against.
- the jig contact surface 141 s continuously extends from the weld surface 142 s in the same plane as the weld surface 142 s of the bus bar weld portion 142.
- the current collector connecting portion 151 of the negative external terminal 105 includes a base portion 151 a extending from the bus bar welded portion 152 along the battery lid 102, and a base portion. It has a negative electrode insertion portion 151b projecting from 151a toward the inside of the battery case, and a seal portion 151c provided on the outer periphery of the negative electrode insertion portion 151b.
- the base portion 151 a is formed such that the length in the direction orthogonal to the wide side plate 101 a gradually decreases as the length approaches the bus bar welded portion 152.
- the surface of the base portion 151a opposite to the battery lid 102 side is an upper die 20 of a jig used for caulking, which will be described later (see FIG. 7).
- the jig contact surface 151 s continuously extends from the weld surface 152 s in the same plane as the weld surface 152 s of the bus bar weld portion 152.
- the positive electrode insertion portion 141b is provided so as to protrude from the base portion 141a toward the inside of the battery container and pass through the through hole 102h of the battery lid 102.
- the positive electrode insertion portion 141b protrudes from the base portion 141a toward the inside of the battery container, and protrudes from the base end insertion portion 141b1 toward the inside of the battery container. It has a cylindrical tip side insertion portion 141b2.
- the outer diameter of the distal end side insertion portion 141b2 is formed to be smaller than the outer diameter of the proximal end insertion portion 141b1, and an abutting step portion 141f is formed between the distal end side insertion portion 141b2 and the proximal end insertion portion 141b1. ing.
- the distal end side insertion portion 141b2 is a portion that is caulked and fixed to the seat surface portion 181 of the positive electrode current collector 180 as described later (see FIG. 7).
- the negative electrode insertion portion 151 b is provided so as to protrude from the base portion 151 a toward the inside of the battery container and pass through the through hole 102 h of the battery lid 102.
- the negative electrode insertion portion 151b protrudes from the base portion 151a toward the inside of the battery case, and has a cylindrical base end side insertion portion 151b1 that protrudes toward the inside of the battery case, and protrudes from the base end side insertion portion 151b1 toward the inside of the battery case. It has a cylindrical tip side insertion portion 151b2.
- the outer diameter of the distal end insertion portion 151b2 is smaller than the outer diameter of the proximal insertion portion 151b1, and a contact step 151f is formed between the distal insertion portion 151b2 and the proximal insertion portion 151b1. ing.
- the distal end side insertion portion 151b2 is a portion that is caulked and fixed to the seat surface portion 191 of the negative electrode current collector 190 as described later (see FIG. 7).
- the distal end side insertion portion 141b2 is provided with a circular recess (hereinafter referred to as an inner recess 141h) formed so as to be recessed from the distal end side toward the proximal end side. It has been.
- the base portion 141a is provided with a circular concave portion (hereinafter referred to as an outer concave portion 141g) formed so as to be recessed from the jig contact surface 141s toward the inside of the battery container.
- the central axes of the outer recess 141g and the inner recess 141h are the same, and the diameter of the outer recess 141g is smaller than the diameter of the inner recess 141h.
- the distal end side insertion portion 151b2 is provided with a circular recess (hereinafter referred to as an inner recess 151h) formed so as to be recessed from the distal end side toward the proximal end side.
- the base portion 151a is provided with a circular recess (hereinafter referred to as an outer recess 151g) formed so as to be recessed from the jig contact surface 151s toward the inside of the battery container.
- the central axes of the outer recess 151g and the inner recess 151h are the same, and the diameter of the outer recess 151g is smaller than the diameter of the inner recess 151h.
- the seal portion 141c of the positive external terminal 104 protrudes from the base portion 141a toward the inside of the battery container on the outer periphery of the proximal end insertion portion 141b1.
- the annular end surface of the seal portion 141c is a surface that presses a flange portion 169b of a gasket 169 described later.
- the annular end surface includes an annular first protrusion 141c1 and a first projection. Two protrusions 141c2 are provided.
- the seal portion 151 c of the negative electrode external terminal 105 protrudes from the base portion 151 a toward the inside of the battery container on the outer periphery of the proximal end insertion portion 151 b 1.
- the annular end surface of the seal portion 151c is a surface that presses a flange portion 169b of a gasket 169 described later.
- the annular end surface includes an annular first protrusion 151c1 and a first protrusion 151c1. Two protrusions 151c2 are provided.
- a pair of through holes through which the base end side insertion portion 141b1 of the positive electrode insertion portion 141b and the base end side insertion portion 151b1 of the negative electrode insertion portion 151b are inserted into the battery lid 102. 102h is provided.
- the external insulator 160 will be described with reference to FIG. 4 and FIG. Since the external insulator 160 on the positive electrode side and the external insulator 160 on the negative electrode side have the same shape, the external insulator 160 on the negative electrode side will be described as a representative.
- the external insulator 160 has a terminal insulating portion 160a, a cover wall 160b, and a through hole 160h into which the gasket 169 is inserted.
- the terminal insulating part 160 a is interposed between the bus bar welded part 152 of the negative electrode external terminal 105 and the battery cover 102 to insulate the negative electrode external terminal 105 and the battery cover 102.
- the covering wall 160b constitutes the outer edge of the external insulator 160, and covers a part of the side surfaces of the bus bar welded portion 152 and the base portion 151a that are exposed to the outside of the battery case in the negative electrode external terminal 105.
- an insulating external insulator 160 is disposed between the battery cover 102 and the positive electrode external terminal 104, and insulation between the positive electrode external terminal 104 and the battery cover 102 is ensured. .
- the gasket 169 will be described with reference to FIG. Since the positive electrode side gasket 169 and the negative electrode side gasket 169 have the same shape, the negative electrode side gasket 169 will be described as a representative.
- the gasket 169 includes a cylindrical tube portion 169a and a flange portion 169b provided at one end of the tube portion 169a. The gasket 169 is attached to the proximal end side insertion portion 151b1 of the negative electrode insertion portion 151b.
- the cylindrical portion 169a of the gasket 169 is disposed so as to be interposed between the through hole 102h of the battery lid 102 and the proximal end side insertion portion 151b1 of the negative electrode insertion portion 151b.
- the flange portion 169b of the gasket 169 is pressed toward the battery lid 102 by the seal portion 151c and is interposed between the outer surface of the battery lid 102 and the annular end surface of the seal portion 151c while being compressed by a predetermined amount. Has been placed.
- the gasket 169 has an insulating property as described above, the negative external terminal 105 and the battery cover 102 are electrically insulated. Similarly, an insulating gasket 169 is disposed on the positive electrode side to seal between the positive external terminal 104 and the battery lid 102.
- annular first protrusions 141c1 and 151c1 and the second protrusions 141c2 and 151c2 shown in FIG. 6A compress the flange 169b of the gasket 169 over the entire circumference, the airtightness inside the battery container is improved. It can be secured.
- positive electrode current collector 180 that electrically connects positive electrode 174 and positive electrode external terminal 104 of wound electrode group 170, and negative electrode 175 and negative electrode external terminal 105 of wound electrode group 170.
- the negative electrode current collector 190 that is electrically connected to each other will be described.
- the positive electrode current collector 180 includes a seat surface portion 181 along the inner surface of the battery lid 102, and is bent at a substantially right angle from the side portion of the seat surface portion 181, while being along the wide side plate 101 a of the battery can 101.
- a flat plate 182 extending toward the bottom plate 101 c of the can 101 and a bonding flat portion 183 connected by an inclined portion 185 provided at the lower end of the flat plate 182 are provided.
- the seat surface portion 181 is provided with a through hole through which the distal end side insertion portion 141b2 of the positive electrode insertion portion 141b is inserted.
- the negative electrode current collector 190 includes a seat surface portion 191 along the inner surface of the battery lid 102, and bends at a substantially right angle from a side portion of the seat surface portion 191, and extends along the wide side plate 101 a of the battery can 101.
- a flat plate 192 extending toward 101c and a bonding flat portion 193 connected by an inclined portion 195 provided at the lower end of the flat plate 192 are provided.
- the seat surface portion 191 is provided with a through hole through which the distal end side insertion portion 151b2 of the negative electrode insertion portion 151b is inserted.
- a rectangular plate-shaped internal insulator 165 is disposed between the seating surface portion 181 of the positive electrode current collector 180 and the battery lid 102 and between the seating surface portion 191 of the negative electrode current collector 190 and the battery lid 102.
- the positive-side internal insulator 165 and the negative-side internal insulator 165 have the same shape, and the positive-side internal insulator 165 is provided with a through-hole through which the proximal-side insertion portion 141b1 of the positive-electrode insertion portion 141b passes.
- the negative electrode side internal insulator 165 is provided with a through hole through which the base end side insertion portion 151b1 of the negative electrode insertion portion 151b passes.
- the positive electrode insertion portion 141b is inserted into the through hole 102h of the battery lid 102 and the through hole of the internal insulator 165 with the gasket 169 attached to the proximal end side insertion portion 141b1.
- the distal end side insertion portion 141b2 of the positive electrode insertion portion 141b is inserted through a through hole formed in the seat surface portion 181 of the positive electrode current collector 180.
- the outer diameter of the base end side insertion portion 141b1 is larger than the diameter of the through hole of the seat surface portion 181 and is a contact step formed between the base end side insertion portion 141b1 and the distal end side insertion portion 141b2.
- the portion 141f is brought into contact with the seat surface portion 181. That is, the base end side insertion portion 141b1 is not inserted into the through hole of the seat surface portion 181.
- a positive crimping portion 141e is formed as shown in FIG.
- the seat surface portion 181 is sandwiched between the positive electrode crimping portion 141e and the contact step portion 141f, and the positive electrode current collector 180 and the positive electrode external terminal 104 are electrically connected.
- the flange portion 169b of the gasket 169 is sandwiched between the seal portion 141c and the outer surface of the battery lid 102, and is held in a compressed state by a predetermined amount.
- the positive crimping portion 141e and the seating surface portion 181 of the positive electrode current collector 180 may be laser welded after being fixed by caulking.
- the negative electrode insertion portion 151b includes a through hole 102h in the battery lid 102 and a through hole in the internal insulator 165 in a state where the gasket 169 is attached to the proximal end side insertion portion 151b1. Is inserted.
- the distal end side insertion portion 151 b 2 of the negative electrode insertion portion 151 b is inserted through a through hole formed in the seat surface portion 191 of the negative electrode current collector 190.
- the outer diameter of the base end side insertion portion 151b1 is larger than the diameter of the through hole of the seat surface portion 191, and the contact step formed between the base end side insertion portion 151b1 and the front end side insertion portion 151b2.
- the portion 151f is brought into contact with the seat surface portion 191. That is, the base end side insertion portion 151 b 1 is not inserted into the through hole of the seat surface portion 191.
- a negative electrode caulking portion 151e is formed as shown in FIG.
- the seat surface portion 191 is sandwiched between the negative electrode caulking portion 151e and the contact step portion 151f, and the negative electrode current collector 190 and the negative electrode external terminal 105 are electrically connected.
- the flange portion 169b of the gasket 169 is sandwiched between the seal portion 151c and the outer surface of the battery lid 102, and is held in a compressed state by a predetermined amount.
- the negative electrode caulking portion 151e and the seating surface portion 191 of the negative electrode current collector 190 may be laser welded after being caulked and fixed.
- the caulking process will be described with reference to FIG. Since the caulking step of the positive electrode insertion portion 141b with respect to the seating surface portion 181 of the positive electrode current collector 180 and the caulking step of the negative electrode insertion portion 151b with respect to the seating surface portion 191 of the negative electrode current collector 190 are similar steps, the negative electrode side is representative. The caulking process will be described. For convenience of explanation, the vertical direction is defined as shown.
- the upper mold 20 of the caulking jig is disposed above the lid assembly 107, and the lower mold 22 of the caulking jig is disposed below the lid assembly 107.
- the upper die 20 of the caulking jig includes a flat plane portion that comes into contact with the jig contact surface 151s of the current collector connection portion 151, and a columnar convex portion 21 that protrudes downward from the plane portion. Yes.
- the lower die 22 of the caulking jig has a conical tip.
- the flat part of the upper mold 20 is brought into contact with the jig contact surface 151s of the base part 151a.
- the upper die 20 may be brought into contact with not only the jig contact surface 151s but also the welding surface 152s.
- the negative electrode external terminal 105 can be easily and accurately positioned with respect to the caulking jig.
- positioned is not formed in the jig
- the negative electrode exterior protrudes upward from the virtual plane V including the welding surface 152s and the jig contact surface 151s (that is, the side opposite to the battery lid 102 side).
- the terminal 105 is not provided. For this reason, the positioning workability of the upper mold 20 of the caulking jig is good.
- the lower mold 22 With the upper mold 20 in contact with the jig contact surface 151s, the lower mold 22 is press-fitted into the inner recess 151h of the negative electrode insertion portion 151b. Thereby, the front-end
- the negative electrode current collector 190, the negative electrode external terminal 105, the gasket 169, the external insulator 160, and the internal insulator 165 are temporarily fixed to the battery lid 102.
- the type of the lower die 22 of the conical shape is sequentially replaced with one having a large tip angle and press-fitted into the inner concave portion 151h of the negative electrode insertion portion 151b, and the tip of the negative electrode insertion portion 151b is gradually expanded outwardly to expand the diameter. .
- the lower mold 22 can be accurately press-fitted into the inner concave portion 151h of the negative electrode insertion portion 151b.
- a flat surface portion 23a having a circular shape in plan view parallel to the battery lid 102 and an inclined portion 23b having an annular shape in plan view that is inclined from the flat surface portion 23a toward the battery cover 102 are provided.
- a mold 23 is prepared. By pressing the lower mold 23 against the tip of the negative electrode insertion portion 151b, the negative electrode caulking portion 151e having an annular shape in plan view is formed. In this way, the negative electrode insertion portion 151b is caulked to the seat surface portion 191 of the negative electrode current collector 190, so that the negative electrode current collector 190, the negative electrode external terminal 105, the gasket 169, the external insulator 160, and the internal insulator 165 are battery lids.
- the positive electrode insertion portion 141b is also caulked to the seat surface portion 181 of the positive electrode current collector 180, so that the positive electrode current collector 180, the positive electrode external terminal 104, the gasket 169, the external insulator 160, and the internal insulator 165 are battery lids. Fastened to 102 and integrated.
- the bus bar welded portion 142 and the current collector connecting portion 141 are integrally arranged on the battery lid 102, and the bus bar welded portion 152 and the current collector connected portion 151 are integrally arranged on the battery lid 102. ing. For this reason, the contact resistance can be reduced, the number of assembling steps for the rectangular secondary battery 100 can be reduced, and the yield can be improved.
- the external terminal is connected to the current collector through a connecting member (caulking member).
- a connecting member caulking member
- the number of parts and the number of connection points on the conduction path are large.
- each of the external terminals 104 and 105 is directly connected to the current collectors 180 and 190, and the number of parts is smaller than that of the secondary battery described in Patent Document 1.
- the construction is simple and the number of connection points is small, so the number of assembly steps can be saved. Further, in the present embodiment, the contact resistance is reduced as compared with the secondary battery described in Patent Document 1.
- the jig contact surface 141s of the positive external terminal 104 extends from the weld surface 142s in the same plane as the weld surface 142s, and the jig contact surface 151s of the negative external terminal 105 is in the same plane as the weld surface 152s. In FIG. For this reason, the workability of the caulking process is good, and the yield of the prismatic secondary battery 100 can be improved.
- the structure in which the bus bar joint portion and the caulking fixing portion are provided in steps are small in area because the caulking jig can be brought into contact with the caulking fixing portion with high accuracy. It was a structure that was difficult to perform caulking. Further, it is conceivable that the bus bar joint portion of the external terminal becomes an obstacle for positioning of the caulking jig, and it takes time for positioning.
- the present embodiment since there is nothing that becomes an obstacle during positioning, workability can be improved. Further, not only the jig contact surfaces 141 s and 151 s but also the welding surfaces 142 s and 152 s can be used for caulking, and the contact area of the caulking jig can be increased, so that the caulking can be performed with high accuracy. be able to.
- the surface (the outer surface on the upper side shown in FIG. 7) of the external terminals 104 and 105 on the side where the upper die 20 of the caulking jig contacts is in addition to the outer recesses 141g and 151g. Is a flat surface parallel to the battery cover 102, but the present invention is not limited to this.
- recesses and holes may be provided, or the jig contact surfaces 141s and 151s may be provided so as to extend from the welding surfaces 142s and 152s through the grooves.
- various shapes that are not formed to protrude to the side on which the upper mold 20 of the caulking jig is disposed can be adopted.
- a protrusion protruding upward from the virtual plane V may be provided at the end of the external terminals 104 and 105 on the center side of the battery case. At least the welding surfaces 142s and 152s, the jig contact surfaces 141s and 151s, and the protrusions protruding upward from the virtual plane V between the welding surfaces 142s and 152s and the jig contact surfaces 141s and 151s are provided.
- the material of the positive electrode external terminal 104, the positive electrode current collector 180, and the positive electrode foil 171 is not limited to aluminum, and may be an aluminum alloy.
- the material of the negative electrode external terminal 105 and the negative electrode current collector 190 is not limited to a copper alloy, and may be copper.
- the material of the negative foil 172 is not limited to copper, and may be a copper alloy.
- both the positive external terminal 104 and the negative external terminal 105 have the same shape, but the present invention is not limited to this. Only one of the positive and negative external terminals 104 and 105 may adopt the shape of the above-described embodiment.
- the present invention is not limited to this.
- the present invention can be applied to various secondary storage devices such as nickel-metal hydride batteries, lithium ion capacitors and electrolytic double layer capacitors.
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- Electrochemistry (AREA)
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Abstract
Description
図1は蓄電素子の一実施の形態としての角形二次電池100の外観斜視図であり、図2は角形二次電池100の構成を示す分解斜視図である。
(1)バスバー溶接部142と集電体接続部141とは電池蓋102上で一体に並設され、バスバー溶接部152と集電体接続部151とは電池蓋102上で一体に並設されている。このため、接触抵抗を低減することができるとともに、角形二次電池100の組立工数を節減し、歩留りを向上することができる。
(1)上記した実施の形態では、外部端子104,105におけるかしめ治具の上型20が当接される側の面(図7に示す上側の外表面)は、外側凹部141g,151gの他は電池蓋102に平行な平坦面とされていたが、本発明はこれに限定されない。外側凹部141g,151gの他に窪みや孔を設けてもよいし、治具当接面141s,151sが溝を介して溶接面142s,152sから延在するように設けられていてもよい。外部端子104,105は、それぞれかしめ治具の上型20を配置する側に突出するものが形成されていない種々の形状を採用することができる。
Claims (4)
- 蓄電素子であって、
電極を有する発電要素と、
前記発電要素を収容する缶と、
前記缶の開口を封止する蓋と、
前記蓋に配置される外部端子と、
前記発電要素の電極と前記外部端子とを接続する集電体とを備え、
前記外部端子は、バスバーが溶接されるバスバー溶接面を有するバスバー溶接部と、かしめ治具当接面を有する集電体接続部とを備え、
前記集電体接続部は、前記蓋の貫通孔に挿通され、先端が前記集電体にかしめ固定された挿通部を備え、
前記バスバー溶接部と前記集電体接続部とは前記蓋上で一体に並設され、
前記治具当接面は、前記バスバー溶接面と同一平面内において、前記バスバー溶接面から延在している蓄電素子。 - 請求項1に記載の蓄電素子において、
前記外部端子には、前記バスバー溶接面と前記かしめ治具当接面とを含む仮想平面から前記蓋側とは反対側に突出するものが設けられていない蓄電素子。 - 請求項1または2に記載の蓄電素子において、
前記挿通部は、前記集電体の貫通孔に挿通される先端側挿通部と、前記集電体の貫通孔に挿通されない基端側挿通部とを有し、
前記基端側挿通部と前記先端側挿通部との間には、前記集電体に当接される当接段部が設けられ、
前記集電体が前記先端側挿通部の先端と前記当接段部とで挟持されるように、前記先端側挿通部の先端が前記集電体にかしめ固定されている蓄電素子。 - 請求項1または2に記載の蓄電素子において、
前記外部端子と前記蓋との間には、前記蓋と前記外部端子との間を封止するシール部材が設けられ、
前記挿通部の外周には、前記シール部材を押圧するシール部が設けられている蓄電素子。
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EP13873839.8A EP2953186B1 (en) | 2013-02-01 | 2013-02-01 | Electricity storage device |
US14/765,360 US9620762B2 (en) | 2013-02-01 | 2013-02-01 | Electrical storage element |
JP2013523111A JP5342090B1 (ja) | 2013-02-01 | 2013-02-01 | 蓄電素子 |
CN201380072043.4A CN105009326B (zh) | 2013-02-01 | 2013-02-01 | 蓄电元件 |
PCT/JP2013/052334 WO2014118965A1 (ja) | 2013-02-01 | 2013-02-01 | 蓄電素子 |
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JP7081929B2 (ja) * | 2018-01-31 | 2022-06-07 | 日東精工株式会社 | 電池用外部端子の製造方法 |
JP7194338B2 (ja) * | 2019-10-10 | 2022-12-22 | トヨタ自動車株式会社 | 二次電池 |
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JP2023519630A (ja) * | 2020-04-09 | 2023-05-11 | 寧徳時代新能源科技股▲分▼有限公司 | エンドカバーアセンブリ、電池セル、電池パック及び装置 |
JP7467674B2 (ja) | 2020-04-09 | 2024-04-15 | 寧徳時代新能源科技股▲分▼有限公司 | エンドカバーアセンブリ、電池セル、電池パック及び装置 |
JP2022146272A (ja) * | 2021-03-22 | 2022-10-05 | プライムプラネットエナジー&ソリューションズ株式会社 | 組電池 |
JP7412384B2 (ja) | 2021-03-22 | 2024-01-12 | プライムプラネットエナジー&ソリューションズ株式会社 | 組電池 |
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US20150380712A1 (en) | 2015-12-31 |
JP5342090B1 (ja) | 2013-11-13 |
US9620762B2 (en) | 2017-04-11 |
CN105009326B (zh) | 2017-07-11 |
EP2953186B1 (en) | 2018-11-28 |
JPWO2014118965A1 (ja) | 2017-01-26 |
CN105009326A (zh) | 2015-10-28 |
EP2953186A4 (en) | 2016-10-05 |
EP2953186A1 (en) | 2015-12-09 |
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