WO2020067375A1 - 蓄電素子の製造方法及び蓄電素子 - Google Patents

蓄電素子の製造方法及び蓄電素子 Download PDF

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Publication number
WO2020067375A1
WO2020067375A1 PCT/JP2019/038033 JP2019038033W WO2020067375A1 WO 2020067375 A1 WO2020067375 A1 WO 2020067375A1 JP 2019038033 W JP2019038033 W JP 2019038033W WO 2020067375 A1 WO2020067375 A1 WO 2020067375A1
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Prior art keywords
electrode
negative electrode
electrode body
laminated
power storage
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PCT/JP2019/038033
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English (en)
French (fr)
Japanese (ja)
Inventor
太郎 山福
健太 中井
純 大山
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GS Yuasa International Ltd
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GS Yuasa International Ltd
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Priority to DE112019004822.8T priority Critical patent/DE112019004822T5/de
Priority to CN201980062779.0A priority patent/CN112753118A/zh
Priority to JP2020549407A priority patent/JP7373134B2/ja
Priority to US17/279,134 priority patent/US12300791B2/en
Publication of WO2020067375A1 publication Critical patent/WO2020067375A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0431—Cells with wound or folded electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/049—Processes for forming or storing electrodes in the battery container
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
    • H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
    • 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
    • H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
    • H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
    • H01M50/627—Filling ports
    • H01M50/636—Closing or sealing filling ports, e.g. using lids
    • H01M50/645—Plugs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for manufacturing a power storage device including an electrode body in which electrodes are stacked, and a power storage device.
  • the power storage device includes a long electrode sheet group 101 and a container 106 in which the electrode sheet group is wound and accommodated.
  • the electrode sheet group 101 is composed of a positive electrode sheet 102 and a negative electrode sheet 103 which are alternately stacked.
  • a lithium electrode sheet 104 is overlaid on the electrode sheet group 101.
  • a separator 105 is provided between the positive electrode sheet 102, the negative electrode sheet 103, and the lithium electrode sheet 104.
  • the power storage device 100 is configured by winding the electrode sheet group 101 and the lithium electrode sheet 104 from one end and storing them in the container 106.
  • a positive electrode sheet 102 constituting a positive electrode is provided on one and the other outermost layers (upper and lower in FIG. 16) of the electrode sheet group 101, respectively.
  • the positive electrode sheet 102 includes a positive electrode current collector 1021 and a positive electrode mixture layer 1022 applied to one surface of the positive electrode current collector 1021.
  • a negative electrode sheet 103 constituting a negative electrode is provided between these positive electrode sheets 102.
  • the negative electrode sheet 103 includes a negative electrode current collector 1031 and a negative electrode mixture layer 1032 coated on both surfaces of the negative electrode current collector 1031.
  • the lithium electrode sheet 104 superimposed on the electrode sheet group 101 includes a lithium electrode current collector 1041 and metal lithium foils 1042 provided on both sides of the lithium electrode current collector 1041.
  • the positive electrode mixture layer 1022 of the positive electrode sheet 102 is coated on the side facing the negative electrode sheet 103.
  • the positive electrode mixture layer 1022 and the negative electrode mixture layer 1032 face each other with the separator 105 interposed therebetween.
  • the electrolytic solution permeates into the separator 105 by injecting the electrolytic solution into the container 106, and the metal lithium foil 1042 of the lithium electrode sheet 104 is dissolved in the electrolytic solution permeated into the separator 105. Then, supply of lithium to the negative electrode mixture layer 1032 of the negative electrode sheet 103 (hereinafter, referred to as precharge) is started.
  • the rate at which the metallic lithium foil 1042 of the lithium electrode sheet 104 dissolves in the electrolytic solution is not sufficient just by impregnating the electrolytic solution into the separator 105, whereby the lithium is deposited on the negative electrode mixture layer 1032 of the negative electrode sheet 103.
  • Supply (precharge) took time.
  • an object of the present embodiment is to provide a method for manufacturing a power storage element in which an alkali metal or an alkaline earth metal used for precharging is rapidly dissolved, and a power storage element.
  • the method for manufacturing a power storage device is a method for manufacturing a power storage device including an electrode having an active material layer, an electrolytic solution, and a case.
  • This manufacturing method A predetermined amount of the electrolytic solution is injected into the case, The predetermined amount is the alkali metal or the alkaline earth metal of the ion supply member in which an alkali metal or an alkaline earth metal is disposed on a conductive member other than the active material layer, and the conductivity of the ion supply member.
  • At least a part of the alkali metal or the alkaline earth metal is immersed in the free electrolytic solution in a state where the alkali metal or the alkaline earth metal is conducted through the conductive member in the case. Dissolves quickly in liquid (electrolyte).
  • the ion supply member may be disposed outside an outermost electrode in a direction in which the electrode assemblies are stacked.
  • the predetermined amount may be an amount in which at least a part of all the layers of the electrodes in the stacked state is in contact with the free electrolyte during the standing.
  • the alkaline earth metal (metal ion) is supplied to each layer (electrode or electrode part) through the free electrolyte, whereby the electrode is precharged efficiently.
  • the electrode body may include a negative electrode as the electrode, a positive electrode, and a separator disposed between the positive electrode and the negative electrode.
  • the negative electrode may have a conductive foil and a negative electrode active material layer laminated on the foil.
  • the ion supply member may include the conductive member and a metal layer including the alkali metal or the alkaline earth metal disposed on the conductive member.
  • the ion supply member may include a laminated portion on which the metal layer is laminated, and a non-laminated portion on which the metal layer is not laminated. The non-laminated portion of the ion supply member may be electrically connected to the foil of the negative electrode in a state where the metal layer faces the negative electrode active material layer via the separator.
  • the electrode body may include the positive electrode and the negative electrode wound around the separator.
  • the separator may be wound around the outermost periphery of the electrode body.
  • the ion supply member may be disposed between the separators in which the laminated portion is wound around the outermost periphery of the electrode body.
  • the negative electrode active material layer may be laminated on both surfaces of the foil of the negative electrode.
  • an outermost peripheral portion of the negative electrode may be disposed outside an outermost peripheral portion of the positive electrode.
  • the ion supply member may be disposed at a curved portion of the electrode body.
  • FIG. 1 is a perspective view of a power storage device according to the present embodiment.
  • FIG. 2 is an exploded perspective view of the power storage device.
  • FIG. 3 is a perspective view illustrating a configuration of an electrode body included in the power storage element.
  • FIG. 4 is a schematic cross-sectional view for explaining the electrode body.
  • FIG. 5 is a perspective view of the ion supply member.
  • FIG. 6 is a sectional view taken along the line VI-VI in FIG.
  • FIG. 7 is a diagram illustrating a mounting position of the ion supply member to the electrode body.
  • FIG. 8 is a sectional perspective view of the liquid injection stopper.
  • FIG. 9 is a diagram for explaining the injection of the electrolytic solution into the case.
  • FIG. 10 is a diagram for explaining the attachment position of the Li pieces in the second embodiment.
  • FIG. 11 is a photograph showing the attachment position of the Li pieces in Example 2.
  • FIG. 12 is a diagram for explaining the attachment position of the Li pieces according to the second embodiment.
  • FIG. 13 is a photograph showing the state of Li pieces 9 days after injection in Example 2.
  • FIG. 14 is a photograph showing the state of Li pieces 13 days after injection in Example 2.
  • FIG. 15 is a perspective view of a power storage device including the power storage element.
  • FIG. 16 is a schematic cross-sectional view of a conventional electrode sheet group.
  • FIG. 17 is a schematic cross-sectional view of a conventional power storage device.
  • the storage element manufactured by the manufacturing method according to the present embodiment includes a primary battery, a secondary battery, a capacitor, and the like.
  • a chargeable / dischargeable secondary battery is described as an example of a power storage element.
  • a configuration of a power storage element manufactured by the manufacturing method according to the present embodiment will be described, and then, a method of manufacturing the power storage element will be described.
  • the names of the components (components) in the present embodiment are those in the present embodiment, and may be different from the names of the components (components) in the background art.
  • members and portions having the same function are described with the same reference numerals.
  • the power storage element manufactured by the manufacturing method according to the present embodiment is a non-aqueous electrolyte secondary battery. More specifically, the power storage element is a lithium ion secondary battery that utilizes electron transfer that occurs with the movement of lithium ions. This type of storage element supplies electric energy. A single or a plurality of power storage elements are used. Specifically, the storage element is used alone when the required output and the required voltage are small. On the other hand, when at least one of the required output and the required voltage is large, the power storage element is used in a power storage device in combination with another power storage element. In the power storage device, a power storage element used in the power storage device supplies electric energy.
  • the electric storage element includes an electrode body 2, a case 3 for accommodating the electrode body 2 together with an electrolytic solution, an external terminal 4 at least partially exposed to the outside, A current collector 5 for connecting to the terminal 4.
  • the electricity storage device 1 also includes an ion supply member 7 that supplies metal ions to the electrode body 2.
  • the power storage element 1 also includes an insulating member 6 and the like disposed between the electrode body 2 and the case 3.
  • the electrolyte is a non-aqueous electrolyte.
  • This electrolytic solution is obtained by dissolving an electrolyte salt in an organic solvent.
  • Organic solvents are, for example, cyclic carbonates such as propylene carbonate and ethylene carbonate, and chain carbonates such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
  • the electrolyte salt is LiClO 4 , LiBF 4 , LiPF 6 or the like.
  • the electrode body 2 has stacked electrodes 23 and 24 as shown in FIG.
  • the electrodes 23 and 24 are stacked by winding the electrodes (the positive electrode 23 and the negative electrode 24) around a winding axis C extending in a predetermined direction.
  • the electrode body 2 includes a core 21, and a stacked body 22 in which the positive electrode 23 and the negative electrode 24 are stacked while being insulated from each other and wound around the core 21.
  • the electrode body 2 of the present embodiment has a separator 25 disposed between the positive electrode 23 and the negative electrode 24.
  • the positive electrode 23 and the negative electrode 24 are wound while being insulated by the separator 25. That is, in the electrode body 2 of the present embodiment, the laminate 22 in which the positive electrode 23, the negative electrode 24, and the separator 25 are stacked is wound.
  • the winding core 21 is usually formed of an insulating material.
  • the core 21 of the present embodiment has a flat cylindrical shape.
  • the core 21 is formed by winding a sheet having flexibility or thermoplasticity.
  • the sheet of the present embodiment is formed of a synthetic resin.
  • the core 21 is not limited to a hollow cylindrical shape, and may be solid. Further, the electrode body 2 may be configured without the core 21.
  • a positive electrode active material layer 232 is laminated on a conductive foil 231.
  • the conductive foil 231 in the positive electrode 23 of the present embodiment is a metal foil.
  • the positive electrode 23 has a strip-shaped metal foil 231 and a positive electrode active material layer 232 laminated on both surfaces of the metal foil 231.
  • the positive electrode active material layer 232 is overlapped on both surfaces of the metal foil 231 with one edge (uncovered portion) in the width direction of the metal foil 231 exposed.
  • the metal foil 231 of the present embodiment is, for example, an aluminum foil.
  • the positive electrode active material layer 232 has a positive electrode active material and a binder.
  • the positive electrode active material of the present embodiment is, for example, a lithium metal oxide.
  • the positive electrode active material is, for example, a composite oxide (LiaCoyO 2 , LiaNixO 2 , LiaMnzO 4 , LiaNixCoyMnzO 2, etc.) represented by LiaMebOc (Me represents one or more transition metals), LiaMeb ( XOc) d (Me represents one or two or more transition metals, and X represents, for example, P, Si, B, V), such as polyanion compounds (LiaFebPO 4 , LiaMbPO 4 , LiaMbSiO 4 , LiaCobPO 4 F, etc. ).
  • the positive electrode active material of the present embodiment is LiNi 1/3 Co 1/3 Mn 1/3 O 2 .
  • the binder used for the positive electrode active material layer 232 is, for example, polyvinylidene fluoride (PVdF), a copolymer of ethylene and vinyl alcohol, polymethyl methacrylate, polyethylene oxide, polypropylene oxide, polyvinyl alcohol, polyacrylic acid, polymethacrylic Acid, styrene butadiene rubber (SBR).
  • PVdF polyvinylidene fluoride
  • SBR styrene butadiene rubber
  • the positive electrode active material layer 232 may further include a conductive additive such as Ketjen Black (registered trademark), acetylene black, and graphite.
  • a conductive additive such as Ketjen Black (registered trademark), acetylene black, and graphite.
  • the positive electrode active material layer 232 of this embodiment has acetylene black as a conductive additive.
  • a negative electrode active material layer 242 is laminated on a conductive foil 241.
  • the conductive foil 241 in the negative electrode 24 of the present embodiment is a metal foil.
  • the negative electrode 24 has a strip-shaped metal foil 241 and a negative electrode active material layer 242 laminated on both surfaces of the metal foil 241.
  • the negative electrode active material layer 242 exposes the other edge (non-covered portion) of the metal foil 241 in the width direction (the side opposite to the non-covered portion of the metal foil 231 of the positive electrode 23) in a state where the metal foil 241 is exposed. 241 are respectively superposed on both surfaces.
  • the metal foil 241 of the present embodiment is, for example, a copper foil.
  • the negative electrode active material layer 242 has a negative electrode active material and a binder.
  • the negative electrode active material is, for example, a carbon material such as graphite, non-graphitizable carbon, and graphitizable carbon, or a material that causes an alloying reaction with lithium ions such as silicon (Si) and tin (Sn).
  • the negative electrode active material of this embodiment is non-graphitizable carbon.
  • the binder used for the negative electrode active material layer 242 is the same as the binder used for the positive electrode active material layer 232.
  • the binder of the present embodiment is polyvinylidene fluoride.
  • the negative electrode active material layer 242 may further include a conductive additive such as Ketjen Black (registered trademark), acetylene black, graphite, or the like.
  • a conductive additive such as Ketjen Black (registered trademark), acetylene black, graphite, or the like.
  • the negative electrode active material layer 242 of this embodiment has no conductive auxiliary.
  • the separator 25 is a member having an insulating property, and is disposed between the positive electrode 23 and the negative electrode 24. Thereby, in the electrode body 2 (specifically, the laminated body 22), the positive electrode 23 and the negative electrode 24 are insulated from each other. The insulation between the positive electrode 23 and the negative electrode 24 does not need to be performed by the separator 25, but is performed by, for example, an insulating layer applied to the surfaces of the electrodes 23 and 24 (on the active material layers 232 and 242). Is also good.
  • the separator 25 holds the electrolytic solution in the case 3. This allows lithium ions to move between the positive electrode 23 and the negative electrode 24 that are alternately stacked with the separator 25 interposed therebetween during charging and discharging of the power storage element 1.
  • the separator 25 has a band shape, and is formed of, for example, a porous film of polyethylene, polypropylene, cellulose, polyamide, or the like.
  • the separator 25 of the present embodiment is provided with an inorganic layer containing inorganic particles such as SiO 2 particles, Al 2 O 3 particles, and boehmite (alumina hydrate) on a substrate formed of a porous film. It is formed with.
  • the base material of the separator 25 of the present embodiment is formed of, for example, polyethylene.
  • the dimension in the width direction of the separator 25 is larger than the width of the negative electrode active material layer 242.
  • the separator 25 is disposed between the positive electrode 23 and the negative electrode 24 that are superposed with the positive electrode active material layer 232 and the negative electrode active material layer 242 being displaced in the width direction so as to overlap in the thickness direction (stacking direction). You. At this time, the uncovered portion of the positive electrode 23 and the uncovered portion of the negative electrode 24 do not overlap.
  • the uncoated portion of the positive electrode 23 protrudes in the width direction (the direction orthogonal to the laminating direction) from the region where the positive electrode 23 and the negative electrode 24 overlap, and the uncoated portion of the negative electrode 24 It protrudes from the overlapping region in the width direction (the direction opposite to the direction in which the uncovered portion of the positive electrode 23 projects).
  • the electrode body 2 is formed by winding the positive electrode 23, the negative electrode 24, and the separator 25 (that is, the stacked body 22) stacked in such a state.
  • the negative electrode 24 is located outside the positive electrode 23 at the outer end of the electrode body 2 in the stacking direction. That is, the positive electrode 23 and the negative electrode 24 are wound such that the negative electrode 24 is located outside the positive electrode 23 at the winding end position when wound around the core 21.
  • the separator 25 is wound around the outermost peripheral portion 24A of the negative electrode 24 (the portion of the negative electrode 24 located at the outermost peripheral position of the electrode body 2 excluding the separator 25).
  • the thickness of the portion corresponding to the outermost peripheral portion of the negative electrode is increased to show the range of the outermost peripheral portion 24A. The thickness is almost the same up to the end.
  • the uncoated laminated portion of the electrode body 2 is formed by a portion where only the uncoated portion of the positive electrode 23 or the uncoated portion of the negative electrode 24 is laminated. 26 are configured.
  • the uncoated laminated portion 26 is a portion that is electrically connected to the current collector 5 in the electrode body 2.
  • the uncoated laminated portion 26 of the present embodiment has two portions (divided uncoated laminated portion) with the hollow portion 27 interposed therebetween when viewed from the direction of the winding axis C of the wound positive electrode 23, negative electrode 24, and separator 25. H.261.
  • the ion supply member 7 supplies metal ions to the negative electrode 24 to supplement the irreversible capacity (initial irreversible capacity) generated in the negative electrode 24 at the time of the initial charge and discharge of the power storage element 1.
  • the ion supply member 7 includes a conductive member 71 and an alkali metal or an alkaline earth metal 72 disposed on the conductive member 71.
  • the conductive member 71 is electrically connected to the electrodes 23 and 24.
  • the ion supply member 7 includes a conductive sheet 71 and a metal layer 72 of an alkali metal or an alkaline earth metal laminated on the sheet 71.
  • the size of the metal layer 72 is set based on the irreversible capacitance.
  • the sheet 71 is a copper foil, and the metal layer 72 is formed of Li.
  • the sheet 71 is a rectangular copper foil, and the metal layer (Li layer) 72 covers one surface of the sheet 71 except one end in the longitudinal direction of the sheet 71. I have.
  • a portion of the ion supply member 7 where the metal layer 72 is stacked is referred to as a stacked portion 73, and a portion where the metal layer 72 is not stacked is referred to as a non-stacked portion 74.
  • This ion supply member 7 is disposed outside the outermost electrode (specifically, the outermost peripheral portion 24A of the negative electrode 24) in the lamination direction of the electrodes 23 and 24 in the electrode body 2. Specifically, in the ion supply member 7, the non-laminated portion 74 is connected (conductive) to the uncoated portion (metal foil 241) of the negative electrode 24 with the metal layer 72 facing the negative electrode active material layer 242 via the separator 25. Is fixed as much as possible). As shown in FIGS. 4 and 7, the ion supply member 7 is also sandwiched between the separators 25 in which the laminated portion 73 is wound outside the outermost peripheral portion 24 ⁇ / b> A of the negative electrode 24.
  • the ion supply member 7 is sandwiched between the first and second layers of the separator 25 wound around the outermost peripheral portion 24A.
  • the metal layer 72 is interposed between the negative electrode active material layer 242 outside the outermost peripheral portion 24A of the negative electrode 24 from the outside in the stacking direction of the laminate 22 (the positive electrode 23, the negative electrode 24, and the separator 25) via the separator 25. Facing each other.
  • the ion supply member 7 of the present embodiment is disposed at a curved portion of the electrode body 2 on the closed portion 311 side of the case 3 (a curved portion below the electrode body 2 in FIGS. 2 and 4).
  • the case 3 includes a case body 31 having an opening, and a cover plate 32 that closes (closes) the opening of the case body 31.
  • an internal space is defined by the case body 31 and the lid plate 32.
  • the case 3 accommodates an electrolytic solution together with the electrode body 2 and the current collector 5 in this internal space.
  • case 3 is formed of a metal having resistance to the electrolytic solution.
  • the case 3 of the present embodiment is formed of, for example, aluminum or an aluminum-based metal material such as an aluminum alloy.
  • the case body 31 includes a plate-shaped closing part 311 and a cylindrical body (peripheral wall) 312 connected to a periphery of the closing part 311.
  • the closing portion 311 is located at the lower end of the case main body 31 when the case main body 31 is arranged with the opening facing upward (that is, the bottom wall of the case main body 31 when the opening faces upward). ) Part.
  • the closing part 311 of the present embodiment has a rectangular shape.
  • the long side direction of the closed portion 311 is defined as the X axis of the rectangular coordinate system
  • the short side direction of the closed portion 311 is defined as the Y axis of the rectangular coordinate system
  • the normal direction of the closed portion 311 is defined as the Z axis of the rectangular coordinate system. I do.
  • the body 312 has a rectangular tube shape, more specifically, a flat rectangular tube shape.
  • the body 312 has a pair of long wall portions 313 extending from a long side at the periphery of the closing portion 311 and a pair of short wall portions 314 extending from a short side at the periphery of the closing portion 311.
  • the short wall portion 314 connects corresponding ends (specifically, opposed in the Y-axis direction) of the pair of long wall portions 313 to form a rectangular tubular body 312.
  • the case main body 31 has a rectangular tube shape (ie, a bottomed rectangular tube shape) in which one end in the opening direction (Z-axis direction) is closed.
  • the electrode body 2 is housed in the case body 31 with the winding axis C oriented in the X-axis direction (see FIG. 2).
  • the lid plate 32 is a member that closes the opening of the case body 31.
  • the contour shape of the lid plate 32 is a shape corresponding to the opening peripheral portion 310 (see FIG. 2) of the case main body 31. That is, the lid plate 32 is a rectangular plate material that is long in the X-axis direction.
  • a liquid injection hole 320 is provided in the cover plate 32 of the present embodiment.
  • the injection hole 320 penetrates the cover plate 32 in the Z-axis direction (thickness direction), and connects the inside of the case 3 to the outside.
  • the injection hole 320 is sealed (sealed) by the injection plug 35. That is, the electric storage element 1 includes the liquid injection plug 35.
  • the injection plug 35 has a head 351 that covers the injection hole 320 and an insertion portion 352 that extends from the head 351.
  • the liquid injection stopper 35 of the present embodiment is fixed to the lid plate 32 by welding the peripheral portion of the head 351 and the lid plate 32 with the insertion portion 352 inserted into the liquid injection hole 320.
  • the case 3 of the present embodiment is formed by joining the peripheral portion of the lid plate 32 and the opening peripheral portion 310 of the case main body 31 in an overlapping state.
  • the opening peripheral portion 310 of the case main body 31 and the peripheral portion of the lid plate 32 are joined by welding.
  • the external terminal 4 is a portion that is electrically connected to an external terminal of another power storage element, an external device, or the like. For this reason, the external terminal 4 is formed of a conductive member. Further, the external terminal 4 is formed of a metal material having high weldability. For example, the external terminal 4 of the positive electrode is formed of an aluminum-based metal material such as aluminum or an aluminum alloy, and the external terminal 4 of the negative electrode is formed of a copper-based metal material such as copper or a copper alloy.
  • the external terminal 4 of the present embodiment is attached to the cover plate 32 with at least a part thereof being exposed to the outside of the case 3. As shown in FIGS. 1 and 2, the external terminal 4 has a surface 41 to which a bus bar or the like can be welded.
  • the current collector 5 is arranged in the case 3 and is directly or indirectly connected to the electrode body 2 in a conductive manner.
  • the current collector 5 of the present embodiment is electrically connected to the electrode body 2 via the clip member 50. That is, the electric storage element 1 includes the clip member 50 that connects the electrode body 2 and the current collector 5 to be conductive.
  • the current collector 5 is formed of a conductive member.
  • the current collector 5 is arranged along the inner surface of the case 3.
  • the current collector 5 electrically connects the external terminal 4 and the clip member 50.
  • the current collector 5 includes a first connection portion 51 that is connected to the external terminal 4 in a conductive manner, and a second connection portion 52 that is connected to the electrode body 2 in a conductive manner.
  • the first connection portion 51 extends along the cover plate 32 from near the boundary between the cover plate 32 and the short wall portion 314 in the case 3, and the second connection portion 52 It extends along the short wall portion 314 from the outer end in the X-axis direction.
  • the second connection part 52 of the present embodiment is joined to the clip member 50 by, for example, ultrasonic welding.
  • the current collector 5 configured as described above is disposed on each of the positive electrode and the negative electrode of the electric storage element 1.
  • the uncoated laminated portion 26 of the positive electrode and the uncoated laminated portion 26 of the negative electrode of the electrode body 2 are arranged.
  • the positive electrode current collector 5 and the negative electrode current collector 5 are formed of different materials.
  • the current collector 5 of the positive electrode is formed of, for example, aluminum or an aluminum alloy
  • the current collector 5 of the negative electrode is formed of, for example, copper or a copper alloy.
  • the clip member 50 sandwiches the positive electrode 23 or the negative electrode 24 stacked in the uncoated laminated portion 26 (specifically, the divided uncoated laminated portion 261) of the electrode body 2 so as to be bundled. Thereby, the clip member 50 electrically connects the non-coated portions of the positive electrode 23 or the non-coated portions of the negative electrode 24 that are laminated in the non-coated laminated portion 26.
  • the clip member 50 of the present embodiment is formed by bending a plate-shaped metal material so that its cross section becomes U-shaped.
  • the insulating member 6 is arranged between the case 3 (specifically, the case main body 31) and the electrode body 2.
  • the insulating member 6 is formed of an insulating resin.
  • the insulating member 6 of the present embodiment is formed by bending a sheet-shaped member having insulating properties and cut into a predetermined shape.
  • the ion supply member 7 is attached to the electrode body 2.
  • the ion supply member 7 is attached to the electrode body 2. Specifically, it is as follows.
  • the core 21 is formed by winding a sheet made of a synthetic resin. Next, the separator 25, the positive electrode 23, the separator 25, and the negative electrode 24 are wound around the core 21 so as to be sequentially stacked.
  • the winding of the separator 25 is continued. That is, even after the positive electrode 23 and the negative electrode 24 have been wound, the separator 25 continues to be wound as it is while winding the ends on the winding end side of the positive electrode 23 and the negative electrode 24. Thereby, the separator 25 is wound (wrapped) around the outermost peripheral portion 24A of the negative electrode 24.
  • the metal layer 72 forms the separator 25 (the separator constituting the first layer).
  • the laminated portion 73 of the ion supply member 7 is disposed on the separator 25 so as to face the negative electrode active material layer 242 via the layer 25), and the non-laminated portion 74 of the ion supply member 7
  • the parts are connected (fixed) by ultrasonic welding, resistance welding, or the like.
  • the separator 25 When the separator 25 is wound a predetermined number of times, the end of the separator 25 on the winding end side is stopped by a tape or the like, whereby the electrode body 2 is completed.
  • the electrode body 2 in a state where the clip member 50 is attached to the divided uncoated laminated portion 261 is attached to the cover plate 32 on which the external terminal 4 and the current collector 5 are assembled.
  • the clip member 50 is attached to the electrode body 2 so as to sandwich the divided uncoated laminated portion 261, and the attached clip member 50 is connected to the second connection portion 52 of the current collector 5 by ultrasonic bonding.
  • the liquid injection plug 35 is not attached to the lid plate 32, that is, the liquid injection hole 320 is opened (not sealed).
  • the electrode body 2 When the electrode body 2, the current collector 5, the external terminals 4, and the like are assembled to the cover plate 32, the insulating member 6 is covered on the electrode body 2, and the cover plate 32 contacts the opening peripheral portion 310 of the case body 31. Until then, the electrode body 2 assembled to the cover plate 32 is inserted into the case main body 31. When the cover plate 32 comes into contact with the opening peripheral portion 310 of the case main body 31, the boundary between the cover plate 32 and the opening peripheral portion 310 of the case main body 31 is welded (laser welding or the like).
  • the free electrolyte solution in the present embodiment is an electrolyte solution that is stored in the lower portion of the case 3 in a state where the electrolyte solution does not permeate the electrode body 2 in the case 3.
  • the predetermined amount refers to the amount of the metal layer 72 of the ion supply member 7 in the free electrolyte that has not soaked into the electrode body 2 (specifically, the separator 25 or the like included in the electrode body 2) in the case 3. It is an amount that at least partially soaks.
  • the electrolytic solution is injected into the case 3 in such an amount that the entire metal layer 72 (laminated portion 73) of the ion supply member 7 is immersed in the free electrolytic solution. That is, as shown in FIG. 9, when the electric storage element 1 is in the posture of the initial charge described later or left for a predetermined time thereafter, the liquid level of the free electrolyte is applied to the ion supply member 7 attached to the electrode body 2.
  • Electrolyte is injected until it is above the upper end of. In this way, by injecting into the case 3 an amount of the electrolytic solution in which the entire metal layer 72 (laminated portion 73) of the ion supply member 7 is immersed in the free electrolyte, the free electrolysis is efficiently performed from the entire metal layer 72. Lithium ions elute in the liquid. As a result, the precharge can proceed in a shorter time.
  • the innermost surfaces of the electrodes 23 and 24 around which the liquid surface of the free electrolyte is wound that is, the electrodes 23 and 24 located at the innermost periphery of the electrode body 2 (in detail, the electrodes 23 and 24)
  • the electrolyte solution is injected until the inner surface (the surface facing the hollow portion 27) of the portions 23 and 24) is positioned at the lower end 24B or more of the side 24S.
  • the first charge (initial charge) of the power storage element 1 is performed in a state where the liquid injection hole 320 is opened (a state before being sealed by the liquid injection plug 35).
  • the posture of the case 3 at this time is the same as the posture at the time of injecting the electrolytic solution, that is, the posture in which the closing portion 311 is located below and the cover plate 32 is located above (see FIG. 9).
  • the liquid injection plug 35 is inserted into the liquid injection hole 320, and the peripheral edge of the head 351 and the peripheral edge of the liquid injection hole 320 of the cover plate 32 are welded, so that the liquid injection hole 320 is formed. Is sealed.
  • the presence or absence of the internal short circuit of the storage element 1 is confirmed.
  • power storage element 1 is left for a predetermined time after charging for confirming an internal short circuit.
  • the predetermined time is a time (a leaving period) for confirming a defective product. For example, specifically, it is left in a room having an ambient temperature of 25 ° C. to 45 ° C. for about 15 hours to 3 days.
  • the voltage will drop sufficiently to a level that can be reliably detected by measurement after passing the idle period.
  • the storage element 1) that causes the above can be reliably selected.
  • the capacity of the electric storage element 1 is confirmed. Specifically, charge / discharge for capacity confirmation is performed.
  • the storage element 1 that can be shipped by sorting based on the voltage measurement at the time of charging and discharging is in a state of waiting for shipment as a completed product.
  • a large irreversible capacity (initial irreversible capacity) mainly occurs during the first charge / discharge cycle (in the example of the present embodiment, charge / discharge for confirming an internal short circuit).
  • Li dissolved in the free electrolyte from the ion supply member 7 (specifically, Li + released from the ion supply member 7) is occluded (precharged) in the negative electrode active material layer 242.
  • the irreversible capacity is suppressed (decreased).
  • the posture of the case 3 during the precharge is the same as the posture during the injection of the electrolytic solution, that is, the posture in which the closing portion 311 is located below and the cover plate 32 is located above. (See FIG. 9).
  • the standing time is preferably 15 hours or more, more preferably 1 day or more, and further preferably 2 days or more.
  • Li + is released into the free electrolyte from the metal layer 72 of the ion supply member 7, and the metal layer 72 gradually decreases.
  • the sheet 71 with the metal layer 72 removed finally remains.
  • metal layer (alkali metal or alkaline earth metal) 72 conducted through electrode body 2 and sheet (conductive member) 71 in case 3 of manufactured power storage element 1. Is immersed in the free electrolyte, at least a part of the metal layer 72 is rapidly dissolved in the free electrolyte, that is, metal ions are rapidly released from the metal layer 72 into the free electrolyte. .
  • the ion supply member 7 is located outside the outermost electrode (specifically, the outermost peripheral portion 24A) in the laminating direction of the electrodes 23 and 24. Are located in For this reason, in the manufactured electric storage element 1, it is possible to prevent a decrease in performance due to a decrease in the area where the electrodes 23 and 24 face each other due to the arrangement of the ion supply member 7 between the electrodes 23 and 24.
  • the position of the case 3 is changed such that the closing portion 311 is positioned below and the cover plate 32 is closed. Is positioned upward (see FIG. 9), the free electrolytic solution is placed at a position equal to or higher than the lower end 24B of the innermost surface (surface facing the hollow portion 27) 24S of the wound electrodes 23 and 24. The liquid level is located. For this reason, Li + (alkali metal or alkaline earth metal dissolved in the free electrolyte) during free electrolysis is supplied to each layer 24 of the electrode body 2 through the free electrolyte, thereby precharging the electrode 24 efficiently. Often done.
  • the distance until the metal ions emitted from the ion supply member 7 arranged on the outer peripheral portion of the electrode body 2 reach the center of the winding of the electrode body 2 can be extremely shortened.
  • the metal ions can be quickly supplied to the center of the winding of the electrode body 2.
  • the storage level is determined for the liquid level of the free electrolyte, the position of the metal layer 72, and the position of the lower end 24B of the innermost surface 24S of the wound electrodes 23 and 24. If the element 1 can be confirmed by X-ray measurement without disassembly, by comparing their heights, whether at least a part of the alkali metal or alkaline earth metal is immersed in the free electrolyte, and It can be checked whether the lower end 24B is in contact with the free electrolyte (that is, whether at least a part of the electrodes 23 and 24 constituting each layer in the stacked state is in contact with the free electrolyte).
  • the power storage device 1 is disassembled and the contents are taken out. The user can check where they were before dismantling.
  • the electrode body 2 taken out is immersed in a solvent (hereinafter, referred to as a mixed solvent) in which ethylene carbonate and diethyl carbonate are mixed at a volume ratio of 1: 1 in a closed vessel, and the inside of the closed vessel is evacuated to form an electrode.
  • a solvent hereinafter, referred to as a mixed solvent
  • the solvent is sufficiently penetrated into the pores of the body 2. 4.
  • the electrode body 2 into which the mixed solvent has sufficiently penetrated is taken out of the closed container, and the electrode body 2 is gradually inserted from the lower end into a container filled with the mixed solvent, and the alkali metal or alkaline earth element of the ion supply member 7 is removed.
  • the sum of the volume of the overflowed mixed solvent obtained in step 3 and the lower end of the alkali metal or alkaline earth metal of the ion supply member 7 when the electrode body 2 is disposed in the case 3, or the electrode 23 in a laminated state , 24 are compared with the inner volume of the case 3 which is equal to or less than the height of the lower end of the layer whose lower end is at the highest position. As a result, the inner volume of the case 3. And the volume of the free electrolyte remaining in the case 3 and 5.
  • the storage element 1 is located at a position equal to or higher than the lower end of the alkali metal or alkaline earth metal of the ion supply member 7, or It can be determined that the liquid surface of the free electrolyte was present at a position where at least a part of the electrodes 23 and 24 constituting each layer is in contact with the free electrolyte.
  • the separator 25 when the separator 25 is wound outside the outermost peripheral portion 24A of the negative electrode 24 when the electrode body 2 is formed, the separator 25 is sandwiched between the separators 25.
  • An ion supply member 7 is provided.
  • the ion supply member 7 can be attached to the manufactured power storage element 1 when the positive electrode 23, the negative electrode 24, and the separator 25 are wound to form the electrode body 2. That is, the formation of the electrode body 2 and the attachment of the ion supply member 7 can be performed simultaneously (in the same process).
  • the ion supply member 7 is sandwiched and fixed by the separator 25, the ion supply member 7 is manufactured when the power storage device 1 is manufactured (for example, when the power storage device 1 is inserted into the case body 31 after being assembled to the cover plate 32). 7 is prevented from coming into contact with other members (such as catching). Thereby, damage to the ion supply member 7 due to the contact can be prevented (suppressed).
  • the metal ions (Li + ) occluded on the outer peripheral side are used for the negative electrode active material. It diffuses (moves) in the material layer 242 and spreads to the center of the winding. Thereby, the metal ions released from the metal layer 72 by the movement in the free electrolyte and the diffusion in the negative electrode active material layer 242 are suitably supplied to the negative electrode active material layer 242 at the center of the winding of the electrode body 2. Is done.
  • the supply of the metal ions to each layer 24 through the free electrolyte is performed more quickly than the diffusion of the metal ions in the negative electrode active material layer 242. For this reason, in the electric storage element 1 manufactured by the manufacturing method of the present embodiment, at least a path of the metal ions by the free electrolyte (specifically, a path through which the metal ions can move quickly outside the electrode body 2) is secured. Just do it.
  • electrode body 2 has negative electrode 24, positive electrode 23, and separator 25 disposed between positive electrode 23 and negative electrode 24 as electrodes.
  • the negative electrode 24 has a conductive foil 241 and a negative electrode active material layer 242 laminated on the foil 241.
  • the ion supply member 7 has a conductive member 71 and a metal layer 72 containing an alkali metal or an alkaline earth metal disposed on the conductive member 71.
  • the ion supply member 7 has a laminated portion 73 on which the metal layer 72 is laminated, and a non-laminated portion 74 on which the metal layer 72 is not laminated.
  • the non-laminated portion 73 is electrically connected to the foil 241 of the negative electrode 24 with the metal layer 72 facing the negative electrode active material layer 242 via the separator 25.
  • the metal ions are supplied to the negative electrode active material layer 242 also through the electrolyte solution permeating the separator 25 from the metal layer 72 of the ion supply member 7 in addition to the above-described path of the metal ions by the free electrolyte solution. Is done. Therefore, supply of metal ions to the negative electrode active material layer 242 can be performed more quickly.
  • positive electrode 23 and negative electrode 24 of electrode body 2 are wound with separator 25 interposed therebetween.
  • the separator 25 is wound around the outermost periphery of the electrode body 2.
  • the ion supply member 7 is disposed between the separators 25 in which the laminated portion 73 is wound around the outermost periphery of the electrode body 2.
  • the negative electrode active material layers 242 are laminated on both surfaces of the foil 241 of the negative electrode 24.
  • the outermost peripheral portion 24 ⁇ / b> A of the negative electrode 24 is disposed outside the outermost peripheral portion of the positive electrode 23. That is, in the outermost peripheral portion 24 ⁇ / b> A of the negative electrode 24, the outer negative electrode active material layer 242 (the negative electrode active material layer laminated on the surface facing the outer peripheral side of the metal foil 241) faces the positive electrode active material layer 232. Therefore, the positive electrode active material layer 232 does not exist in the metal ion supply path from the metal layer 72 of the ion supply member 7 to the negative electrode active material layer 242 through the separator 25.
  • the ion supply member 7 is disposed at a curved portion of the electrode body 2 (a curved portion below the electrode body 2 in FIGS. 2 and 4). By doing so, the ion supply member 7 can be more firmly fixed by applying tension (therefore, the metal layer 72 can be surely opposed to the negative electrode active material layer 242 via the separator 25). Metal ions can be more reliably supplied to the negative electrode active material layer 242.
  • Example 1 Here, experimental conditions and experimental results of an experiment performed to confirm the effect of the method for manufacturing the electric storage device 1 of the above embodiment are shown below.
  • ⁇ Experiment conditions> (1) A Li metal foil was attached to four identically configured electrode bodies (winding type electrode bodies) A to D under the following conditions. Electrode body A: Li metal foil was stuck on the negative electrode active material layer. Electrode body B: A Li metal foil was stuck on a copper foil electrically connected to the negative electrode. Electrode C: Li metal foil was stuck on the negative electrode active material layer. Electrode body D: A Li metal foil was stuck on a copper foil electrically connected to the negative electrode.
  • Electrode A Almost no precharge was possible.
  • Electrode B Almost no precharge was possible.
  • Electrode C Precharge was slightly advanced, but did not end 13 days after injection. Electrode body D: Precharge was completed 13 days after injection. (It was confirmed that the attached Li metal foil had completely reacted and disappeared. The Li metal foil remained 9 days after the injection.)
  • Example 2 The following experiment was also performed. ⁇ Experiment conditions> (1) In this experiment, as shown in FIG. 10 and FIG. 11, in the electrode body a, a Li piece 75 having a thickness of 3 mm was attached to three places of the current collector 5 connected to the electrode body a. As shown in FIG. 12, in the electrode body b, a 3 mm-thick Li piece 75 is attached on the negative electrode active material layer 242, and the outside thereof is surrounded by the separator 25. (2) The electrode bodies a and b are placed in a transparent resin bag, and the electrolyte bag is injected into the resin bag until the electrode bodies a and b are immersed. Then, the resin bag is sealed.
  • Electrode body a -3 days after injection The reduction of Li pieces was at a level that could not be visually observed. 9 days after injection: As shown in the photograph of FIG. 13, it was confirmed that the Li pieces were reduced. -13 days after injection: The Li fragments adhered to the site surrounded by the circle in the photograph of Fig. 14 had completely disappeared due to the reaction. (2) Electrode body b -It was confirmed that Li pieces remained 13 days after the injection.
  • the method for manufacturing a power storage device of the present invention is not limited to the above embodiment, and it is needless to say that various changes can be made without departing from the spirit of the present invention.
  • the configuration of another embodiment can be added to the configuration of one embodiment, and a part of the configuration of one embodiment can be replaced with the configuration of another embodiment. Further, a part of the configuration of an embodiment can be deleted.
  • the metal forming the metal layer 72 of the ion supply member 7 is Li, but is not limited to this structure. That is, the metal forming the metal layer 72 is not limited to the metal included in the negative electrode active material layer 242.
  • the metal constituting the metal layer 72 is one that eliminates or reduces the irreversible capacity in the power storage element 1 by being occluded in the negative electrode active material layer 242 when released into the electrolyte as metal ions.
  • An alkali metal or an alkaline earth metal that is not included in the negative electrode active material layer 242 may be used.
  • the specific configuration of the alkali metal or alkaline earth metal disposed on conductive member 71 is not limited. That is, the alkali metal or the alkaline earth metal may not be a sheet (foil) like the metal layer 72 of the above embodiment.
  • the conductive member 71 is formed of a porous body, an alkali metal or an alkaline earth metal may be filled in the pores of the porous body. That is, the alkali metal or the alkaline earth metal only needs to be disposed on the conductive member 71 in a state of being electrically connected to the electrodes 23 and 24.
  • the conductive member (the sheet in the example of the above embodiment) 71 of the ion supply member 7 is electrically connected to the negative electrode 24, but is not limited to this configuration.
  • the conductive member 71 may be in conduction with the positive electrode 23. That is, the conductive member 71 has a configuration in which an alkali metal or an alkaline earth metal (the metal layer 72 in the example of the above embodiment) disposed on the conductive member 71 is electrically connected to the electrode (the positive electrode 23 or the negative electrode 24). I just need.
  • the specific configuration of the conductive member 71 is not limited.
  • the conductive member 71 of the above-described embodiment has a sheet shape, but may be configured by the case 3 that is in conduction with the electrodes 23 and 24.
  • the metal layer 72 is disposed on the inner surface of the case 3, and the ion supply member 7 includes the metal layer 72 and the case 3.
  • the conductive member 71 may be configured by a current collector 5 that connects the electrode body 2 and the external terminal 4.
  • the metal layer 72 is disposed on the current collector 5, and the ion supply member 7 includes the metal layer 72 and the current collector 5. That is, the conductive member 71 may have any configuration as long as the metal layer 72 is electrically connected to the electrodes 23 and 24.
  • the conductive member 71 is connected to the non-coated portion of the negative electrode 24 so as to be able to conduct, but is not limited to this configuration.
  • the conductive member 71 may be connected to any one of the members 23 and 24 in the case 3 in a conductive state.
  • the ion supply member 7 has the stacked portion 73 and the non-stacked portion 74, but is not limited to this configuration.
  • the ion supply member 7 may be only the lamination portion 73.
  • the surface of the conductive member (sheet) 71 opposite to the surface on which the metal layer 72 is laminated is connected to the electrodes 23 and 24 and the like so as to be conductive.
  • the surface of the sheet 71 on the side opposite to the surface on which the metal layer 72 is stacked in the portion forming the stacked portion 73 is the electrode 23, 24 and the like.
  • the conductive member 71 of the ion supply member 7 is a copper foil, but is not limited to this configuration.
  • the conductive member 71 may be made of a material having conductivity and resistance to an electrolyte.
  • the shape (contour) of the conductive member (sheet) 71 is not limited to a rectangular shape, and various shapes can be selected.
  • the ion supply member 7 (specifically, the laminated portion 73) is arranged between the separators 25, but is not limited to this configuration.
  • the separator 25 may not be provided outside the ion supply member 7. Further, the ion supply member 7 (laminated portion 73) may directly face the negative electrode active material layer 242 without the interposition of the separator 25.
  • the arrangement position of the ion supply member 7 is not limited to the outside of the outermost peripheral portion 24A of the negative electrode 24.
  • the ion supply member 7 may be arranged at an intermediate position (for example, between the positive electrode 23 and the negative electrode 24) in the laminating direction of the electrode body 2.
  • the ion supply member 7 is connected to the negative electrode 24 by the non-laminated portion 74, and is insulated from the positive electrode 23 by the separator 25 and the like.
  • the amount of the electrolyte solution injected into the case 3 is such that the winding axis C is horizontal or substantially horizontal (orthogonal or approximately orthogonal to the direction of gravity). Is disposed, at least a part of the metal layer 72 of the ion supply member 7 is immersed in the free electrolyte, and at a position higher than the lower end 24B of the innermost peripheral surface 24S of the electrode 24 of the electrode body 2.
  • the amount is the level at which the level of the free electrolytic solution is located, but is not limited to this configuration.
  • the amount of the electrolytic solution injected into the case 3 depends on the number of the electrodes 24 constituting each layer in the laminated state (for example, a sheet-like electrode in a laminated electrode body) in the electrode body 2 in which the electrodes 24 are laminated. Alternatively, at least a part of each of the electrode parts (for example, the part of the electrode 24 constituting each layer in the wound electrode body 2) may be in an amount that comes into contact with the free electrolyte. For example, the amount of the electrolytic solution injected into the case 3 is determined when the electric storage element 1 is arranged such that the winding axis C is vertical or substantially vertical (same or substantially the same as the direction of gravity).
  • At least a part of the metal layer 72 of the supply member 7 is immersed in the free electrolyte, and the liquid surface of the free electrolyte is located at a position equal to or higher than the lower end of the electrode 24 constituting each layer in the so-called wound electrode body 2. (That is, the lower ends of all the layers are immersed in the free electrolyte).
  • the electricity storage element 1 is arranged so that the winding axis C is vertical or substantially vertical (same or substantially the same as the direction of gravity), the alkali dissolved in the free electrolyte from the ion supply member 7 can be obtained.
  • the metal or alkaline earth metal (metal ion) is supplied to each layer of the electrode body 2 (the whole area in the longitudinal direction of the electrode 24) through the free electrolyte, whereby the electrode 24 is precharged efficiently. That is, compared to the case where the precharged metal ions move (diffuse) in the negative electrode active material layer 242 or move in the electrolytic solution impregnated in the separator 25, the ions arranged on the outer peripheral portion of the electrode body 2 The distance required for the metal ions released from the supply member 7 to reach the center of the winding of the electrode body 2 can be extremely shortened by moving through the free electrolytic solution. The metal ions can be quickly supplied to the center of the winding of the electrode body 2.
  • the electrode body 2 of the power storage device 1 of the above embodiment is a so-called wound type, but is not limited to this configuration.
  • the electrode body 2 may be a so-called stacked type in which sheet-like electrodes (positive electrode, negative electrode) are stacked in the thickness direction of each electrode.
  • the amount of the electrolytic solution injected into the case 3 is set such that the lamination direction of the electrodes (positive electrode, negative electrode) in the electrode body is horizontal or substantially horizontal (orthogonal or substantially orthogonal to the direction of gravity).
  • the free electrolyte is placed at a position equal to or higher than the lower end of each electrode (negative electrode) in the so-called stacked electrode body.
  • the amount is preferably such that the liquid surface is located (that is, the lower ends of all the electrodes (negative electrodes) are immersed in the free electrolyte).
  • the alkali metal or alkaline earth metal (metal ion) dissolved in the free electrolyte from the ion supply member 7 Is supplied to each electrode (negative electrode) of the electrode body through the free electrolytic solution, whereby the electrode is precharged efficiently.
  • At least one of the positive electrode 23 and the negative electrode 24 may be folded in a zigzag manner (may be folded in a bellows shape).
  • the specific location of the ion supply member 7 on the electrode body 2 is not limited.
  • the ion supply member 7 of the above embodiment is arranged at the lower curved portion of the electrode body 2, for example, it may be arranged at the upper curved portion (opposite to the curved portion). (For example, a portion between the upper and lower curved portions in FIGS. 2 and 4).
  • the formation of the electrode body 2 and the attachment of the ion supply member 7 to the electrode body 2 are performed simultaneously (in the same process), but the present invention is not limited to this configuration.
  • the configuration in which the ion supply member 7 is attached to the electrode body 2, that is, the step of forming the electrode body 2 and the step of attaching the ion supply member 7 to the electrode body 2 may be separate.
  • the injection hole 320 is provided in the cover plate 32, but may be provided in the case body 31.
  • a storage element (for example, a storage element before precharge) including the ion supply member 7 provided is provided.
  • the ion supply member 7 of the electric storage element 1 has a conductive member 71 and a metal layer 72 containing an alkali metal or an alkaline earth metal disposed on the conductive member 71.
  • the conductive member 71 is electrically connected to the negative electrode 24.
  • the electrolytic solution includes a free electrolytic solution that does not permeate the electrode body 2 in the case 3.
  • the predetermined amount is an amount at which at least a part of the metal layer 73 contacts the free electrolyte solution.
  • the electrode body 2 has a separator 25 disposed between the positive electrode 23 and the negative electrode 24.
  • the negative electrode 24 has a conductive foil 241 and a negative electrode active material layer 242 laminated on the foil 241.
  • the ion supply member 7 has a laminated portion 73 on which the metal layer 72 is laminated, and a non-laminated portion 74 on which the metal layer 72 is not laminated. In the ion supply member 7, the non-laminated portion 73 is electrically connected to the foil 241 of the negative electrode 24 with the metal layer 72 facing the negative electrode active material layer 242 via the separator 25.
  • the electrode body 2 has a positive electrode 23 and a negative electrode 24 wound around a separator 25.
  • the separator 25 is wound around the outermost periphery of the electrode body 2.
  • the ion supply member 7 is disposed between the separators 25 in which the laminated portion 73 is wound around the outermost periphery of the electrode body 2.
  • the negative electrode active material layer 242 is laminated on both surfaces of the foil 241 of the negative electrode 24.
  • the outermost peripheral portion 24 ⁇ / b> A of the negative electrode 24 is disposed outside the outermost peripheral portion of the positive electrode 23.
  • the ion supply member 7 is disposed at a curved portion of the electrode body 2.
  • Conductive member 71 of power storage element 1 is electrically connected to negative electrode 24.
  • the electrolytic solution includes a free electrolytic solution that does not permeate the electrode body 2 in the case 3.
  • the predetermined amount is an amount at which at least a part of the conductive member 71 contacts the free electrolyte.
  • the electrode body 2 has a separator 25 disposed between the positive electrode 23 and the negative electrode 24.
  • the negative electrode 24 has a conductive foil 241 and a negative electrode active material layer 243 laminated on the foil 241.
  • the conductive member 71 has a first portion 73 and a second portion 74. In the conductive member 71, the second portion 74 is electrically connected to the foil 241 of the negative electrode 24 with the first portion 73 facing the negative electrode active material layer 242 via the separator 25.
  • the electrode body 2 has a positive electrode 23 and a negative electrode 24 wound around a separator 25.
  • the separator 25 is wound around the outermost periphery of the electrode body 2.
  • the conductive member 71 is disposed between the separators 25 in which the first portion 73 is wound around the outermost periphery of the electrode body 2.
  • the negative electrode active material layer 242 is laminated on both surfaces of the foil 241 of the negative electrode 24.
  • the outermost peripheral portion 24 ⁇ / b> A of the negative electrode 24 is disposed outside the outermost peripheral portion of the positive electrode 23.
  • the conductive member 71 is disposed at a curved portion of the electrode body 2.
  • the power storage element is used as a chargeable / dischargeable non-aqueous electrolyte secondary battery (for example, a lithium ion secondary battery) has been described.
  • the type and size (capacity) of the power storage element are arbitrary It is.
  • a lithium ion secondary battery has been described as an example of a power storage element, but the present invention is not limited to this.
  • the present invention can be applied to various secondary batteries, primary batteries, and power storage elements of capacitors such as electric double layer capacitors.
  • the power storage element (for example, a battery) 1 may be used for a power storage device (a battery module when the power storage element is a battery) 11 as shown in FIG.
  • the power storage device 11 includes at least two power storage elements 1 and a bus bar member 12 that electrically connects the two (different) power storage elements 1 to each other. In this case, the technology of the present invention only needs to be applied to at least one storage element 1.
  • SYMBOLS 1 Electric storage element, 2 ... Electrode body, 21 ... Core, 22 ... Laminated body, 23 ... Positive electrode (electrode), 231 ... Metal foil (conductive foil), 232 ... Positive electrode active material layer, 24 ...
  • Negative electrode ( 241, a negative electrode active material layer; 24A, an outermost peripheral portion; 24B, a lower end of an innermost surface; 24S, an innermost periphery of a wound electrode;

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
PCT/JP2019/038033 2018-09-26 2019-09-26 蓄電素子の製造方法及び蓄電素子 Ceased WO2020067375A1 (ja)

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DE112019004822.8T DE112019004822T5 (de) 2018-09-26 2019-09-26 Verfahren zur herstellung einer energiespeichereinrichtung und energiespeichereinrichtung
CN201980062779.0A CN112753118A (zh) 2018-09-26 2019-09-26 蓄电元件的制造方法和蓄电元件
JP2020549407A JP7373134B2 (ja) 2018-09-26 2019-09-26 蓄電素子の製造方法及び蓄電素子
US17/279,134 US12300791B2 (en) 2018-09-26 2019-09-26 Method for manufacturing energy storage device, and energy storage device

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US12300791B2 (en) 2025-05-13
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JPWO2020067375A1 (ja) 2021-09-02
JP7373134B2 (ja) 2023-11-02

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