WO2024057726A1 - Élément de stockage d'énergie - Google Patents

Élément de stockage d'énergie Download PDF

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Publication number
WO2024057726A1
WO2024057726A1 PCT/JP2023/027085 JP2023027085W WO2024057726A1 WO 2024057726 A1 WO2024057726 A1 WO 2024057726A1 JP 2023027085 W JP2023027085 W JP 2023027085W WO 2024057726 A1 WO2024057726 A1 WO 2024057726A1
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Prior art keywords
electrode body
hole
positive electrode
electrode
separator
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PCT/JP2023/027085
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English (en)
Japanese (ja)
Inventor
義人 ▲高▼木
一弥 岡部
良一 奥山
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株式会社Ｇｓユアサ
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Publication of WO2024057726A1 publication Critical patent/WO2024057726A1/fr

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    • 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
    • H01G11/66—Current collectors
    • H01G11/70—Current collectors characterised by their structure
    • 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
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • 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
    • 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
    • H01M10/0587—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte

Definitions

  • the present invention relates to a power storage element in which an electrode body and an electrolyte are housed in a container.
  • Patent Document 1 discloses a wound-type electrode body formed by laminating and winding a positive electrode plate and a negative electrode plate with a separator interposed therebetween, and a wound-type power storage device (power storage element) in which an electrolytic solution is housed in a battery container. Disclosed.
  • a power storage element including a conventional wound-type electrode body as described above, it may be difficult to allow the electrolyte to penetrate into the electrode body when injecting the electrolyte into the container.
  • an electrolyte injection part is provided on the wall of the container that extends in the direction of the winding axis of the electrode body, it is difficult for the electrolyte to penetrate from the outside to the inside of the electrode body. becomes difficult. In particular, if the length of the electrode body in the direction of the winding axis is long, it becomes more difficult to infiltrate the electrolyte into the electrode body.
  • the present invention was made by the inventors of the present application newly paying attention to the above-mentioned problem, and an object of the present invention is to provide a power storage element in which an electrolytic solution can easily penetrate into an electrode body.
  • a power storage element includes an electrode body in which an electrode plate and a separator are wound, an electrolytic solution, and a container in which the electrode body and the electrolytic solution are housed, and the container includes the
  • the electrode body has an injection part for the electrolytic solution on a wall extending in the winding axis direction, the electrode body has a length in the winding axis direction of 500 mm or more, and the separator has a base material and a base material. and an inorganic coat layer containing inorganic particles coated on the base material.
  • the electrolyte can easily penetrate into the electrode body.
  • FIG. 1 is a perspective view showing the appearance of a power storage element according to an embodiment.
  • FIG. 2 is an exploded perspective view showing each component of the power storage device according to the embodiment.
  • FIG. 3 is a perspective view showing the structure of the electrode body according to the embodiment.
  • FIG. 4 is a perspective view and a cross-sectional view showing the structure of an electrode body according to an embodiment.
  • FIG. 5 is a front view and a cross-sectional view showing the configuration of a through hole of an electrode body according to an embodiment.
  • FIG. 6 is a front view and a cross-sectional view showing the structure of a through hole of an electrode body according to Modification 1 of the embodiment.
  • a power storage element includes an electrode body in which an electrode plate and a separator are wound, an electrolytic solution, and a container in which the electrode body and the electrolytic solution are housed, the container has an injection part for the electrolytic solution on a wall extending in the direction of the winding axis of the electrode body, the electrode body has a length of 500 mm or more in the direction of the winding axis, and the separator has: It has a base material and an inorganic coat layer containing inorganic particles coated on the base material.
  • the power storage element includes a wound electrode body, and an electrolyte injection part is provided in a wall portion of the container that extends in the direction of the winding axis of the electrode body. This makes it difficult for the electrolyte to penetrate from the outside to the inside of the electrode body when pouring the electrolyte into the container, making it difficult for the electrolyte to penetrate into the electrode body.
  • By coating the separator with the electrolyte it is possible to improve the permeability of the electrolyte into the separator.
  • the length of the electrode body in the direction of the winding axis is 500 mm or more, it becomes more difficult to penetrate the electrolyte into the electrode body, so by coating the separator with an inorganic coating layer, it is possible to The effect of improving the permeability of the electrolyte becomes remarkable. Therefore, the time required for the electrolyte to penetrate into the electrode body can be shortened, so that the electrolyte can easily penetrate into the electrode body.
  • the inorganic coat layer may have a permeation area of 80 mm 2 or more for the electrolyte at 300 seconds after the electrolyte is dropped.
  • the inorganic coating layer coated on the separator has a relatively short electrolytic solution penetration area of 80 mm 2 or more at 300 seconds after the electrolytic solution is dropped. It is an inorganic coating layer that can permeate a relatively wide area over time. In this way, by using an inorganic coating layer that allows the electrolyte to permeate a relatively wide area in a relatively short period of time, the permeability of the electrolyte into the separator can be improved.
  • the inorganic coat layer may include at least one of barium sulfate and alumina as the inorganic particles.
  • the inventors of the present invention have discovered that when an electrolyte is dropped onto an inorganic coat layer containing at least one of barium sulfate and alumina, the electrolyte can penetrate a relatively wide area of the inorganic coat layer in a relatively short time. According to the power storage element described in (3) above, by including at least one of barium sulfate and alumina in the inorganic coating layer coated on the separator, the permeability of the electrolyte into the separator can be improved.
  • the electrode body may have a length of 600 mm or more in the direction of the winding axis.
  • the inventors of the present application have found that even when using the electrode body, by coating the separator with an inorganic coating layer, the electrolytic solution can be easily penetrated into the electrode body. Therefore, when a long electrode body like the electricity storage element described in (4) above is used, the effect of adopting the configuration of the present application is high.
  • a through hole may be formed in the electrode plate.
  • the separator in which the permeability of the electrolytic solution has been improved by the inorganic coating layer, passes through the through hole to the electrode. Allows electrolytes to penetrate the body.
  • the direction in which the short sides of the container face each other is defined as the X-axis direction.
  • the direction in which the long sides of the container face each other or the thickness direction of the container is defined as the Y-axis direction.
  • the direction in which the container body and lid of the container are lined up or the vertical direction is defined as the Z-axis direction.
  • X-axis direction, Y-axis direction, and Z-axis direction are directions that intersect with each other (orthogonal in this embodiment).
  • the Z-axis direction may not be the vertical direction, but for convenience of explanation, the Z-axis direction will be described as the vertical direction below.
  • the X-axis plus direction indicates the arrow direction of the X-axis
  • the X-axis minus direction indicates the opposite direction to the X-axis plus direction.
  • the X-axis direction it refers to both or one of the X-axis plus direction and the X-axis minus direction.
  • One side and the other side in the X-axis direction refer to one and the other of the X-axis plus direction and the X-axis minus direction.
  • Expressions indicating relative directions or orientations, such as parallel and orthogonal, include cases where the directions or orientations are not strictly speaking.
  • FIG. 1 is a perspective view showing the appearance of a power storage element 10 according to the present embodiment.
  • FIG. 2 is an exploded perspective view showing each component of the power storage element 10 according to the present embodiment.
  • the power storage element 10 is a secondary battery (single battery) that can charge and discharge electricity, and more specifically, it is a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery.
  • the power storage element 10 is used as a battery for driving or starting an engine of a moving object such as an automobile, a motorcycle, a watercraft, a ship, a snowmobile, an agricultural machine, a construction machine, or a railway vehicle for an electric railway.
  • Examples of the above-mentioned vehicles include electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and fossil fuel (gasoline, diesel oil, liquefied natural gas, etc.) vehicles.
  • Examples of the above-mentioned railway vehicles for electric railways include electric trains, monorails, linear motor cars, and hybrid electric trains equipped with both a diesel engine and an electric motor.
  • the power storage element 10 can also be used as a stationary battery used for home or business use.
  • the power storage element 10 is not limited to a non-aqueous electrolyte secondary battery, and may be a secondary battery that is not a non-aqueous electrolyte secondary battery, or may be a capacitor.
  • the power storage element 10 may be not a secondary battery but a primary battery that allows the user to use the stored electricity without charging it.
  • the power storage element 10 may be a pouch type power storage element.
  • a rectangular parallelepiped-shaped (prismatic) power storage element 10 that is flat in the Y-axis direction is illustrated, but the shape of the power storage element 10 is not limited to a rectangular parallelepiped shape, and may include a polygonal prism shape other than a rectangular parallelepiped, The shape may be an elongated cylinder, an elliptical cylinder, a cylinder, or the like.
  • the power storage element 10 includes a container 100, a pair of terminals 300 (positive electrode and negative electrode), and a pair of upper gaskets 400 (positive electrode and negative electrode). As shown in FIG. 2, inside the container 100, a pair of lower gaskets 500 (positive electrode and negative electrode), a pair of current collectors 600 (positive electrode and negative electrode), and an electrode body 700 are accommodated. . In addition to the above-mentioned components, a spacer placed on the side or below the electrode body 700, an insulating film that wraps around the electrode body 700, etc. may be placed.
  • An electrolytic solution (non-aqueous electrolyte) is sealed inside the container 100, but illustration thereof is omitted.
  • the type of electrolytic solution is not particularly limited as long as it does not impair the performance of the power storage element 10, and various types can be selected.
  • the electrolytic solution includes a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the non-aqueous solvent can be appropriately selected from known non-aqueous solvents.
  • non-aqueous solvents examples include cyclic carbonates such as ethylene carbonate (EC) or propylene carbonate (PC), chain carbonates such as ethyl methyl carbonate (EMC), carboxylic acid esters, phosphoric acid esters, sulfonic acid esters, ethers, amides, Examples include nitrile.
  • cyclic carbonates such as ethylene carbonate (EC) or propylene carbonate (PC)
  • chain carbonates such as ethyl methyl carbonate (EMC)
  • carboxylic acid esters examples include phosphoric acid esters, sulfonic acid esters, ethers, amides
  • the electrolyte salt can be appropriately selected from known electrolyte salts.
  • the electrolyte salt include lithium salts such as inorganic lithium salts such as LiPF 6 , sodium salts, potassium salts, magnesium salts, onium salts, and the like. Among these, lithium salts are preferred.
  • the container 100 is a rectangular parallelepiped-shaped (prismatic or box-shaped) case that has a container body 110 with an opening formed in the positive Z-axis direction and a lid 120 that closes the opening of the container body 110.
  • the lid 120 is a flat, rectangular member that constitutes the lid of the container 100, and is arranged in the positive Z-axis direction of the container body 110.
  • the lid body 120 is an example of a wall portion extending in the direction of the winding axis of the electrode body 700.
  • the winding axis direction of the electrode body 700 is the direction in which the winding axis L of the electrode body 700, which will be described later, extends (the direction along the winding axis L, in this embodiment, the X-axis direction).
  • the container body 110 is a member that constitutes the main body of the container 100 and includes a rectangular cylindrical portion and a bottom.
  • the container body 110 has a pair of long side walls 111 on both sides in the Y-axis direction, a pair of short side walls 112 on both sides in the X-axis direction, and has a pair of short side walls 112 on both sides in the Y-axis direction. It has a bottom wall portion 113 on the surface (bottom surface).
  • the long side wall portion 111 is a flat rectangular wall portion extending in the X-axis direction (the direction of the winding axis of the electrode body 700), and constitutes the long side surface of the container 100.
  • the long side wall 111 is adjacent to the short side wall 112, the bottom wall 113, and the lid 120, and has a larger area than the short side wall 112.
  • the short side wall portion 112 is a flat rectangular wall portion extending in the Z-axis direction, and constitutes a short side surface of the container 100.
  • the short side wall 112 is adjacent to the long side wall 111, the bottom wall 113, and the lid 120, and has a smaller area than the long side wall 111.
  • the bottom wall portion 113 is a flat, rectangular wall portion that extends in the X-axis direction (the direction of the winding axis of the electrode body 700), and constitutes the bottom surface of the container 100.
  • the bottom wall portion 113 is disposed adjacent to the long side wall portion 111 and the short side wall portion 112.
  • the container main body 110 and the lid 120 are joined by welding or the like, so that the inside of the container 100 is hermetically sealed.
  • the material of the container 100 is not particularly limited, and may be a weldable (joinable) metal such as stainless steel, aluminum, aluminum alloy, iron, or plated steel plate, or resin may be used.
  • the container body 110 and the lid 120 may be made of the same material or may be made of different materials.
  • the power storage element 10 is a pouch type power storage element
  • the container 100 may be a laminate film made of multiple layers including a metal layer and a resin layer.
  • a liquid injection part 130 and a gas discharge valve 140 are formed in the container 100.
  • the liquid injection part 130 and the gas discharge valve 140 are formed on the lid 120. That is, the liquid injection part 130 and the gas discharge valve 140 are formed on a wall portion extending in the winding axis direction (X-axis direction) of the electrode body 700.
  • the gas discharge valve 140 is a safety valve that releases the pressure inside the container 100 when the pressure increases excessively.
  • the gas exhaust valve 140 is arranged at the center in the X-axis direction and the center in the Y-axis direction of the lid 120, but it may be arranged at any position on the lid 120.
  • the liquid injection part 130 is a part (electrolyte liquid injection part) for injecting the electrolytic solution into the inside of the container 100 when manufacturing the power storage element 10.
  • the liquid injection unit 130 evacuates the inside of the container 100 , injects an electrolytic solution into the container 100 to impregnate the electrode body 700 with the electrolytic solution, and performs functions such as filling the electrode body 700 with the electrolytic solution when manufacturing the power storage element 10 . It is used to evacuate gas from inside.
  • the liquid injection part 130 is arranged at the center of the lid 120 in the negative X-axis direction and the Y-axis direction, but it may be arranged at any position on the lid 120.
  • the liquid injection part 130 includes a liquid injection port 131 and a liquid injection plug 132.
  • the liquid injection port 131 is, for example, a circular through hole formed in the lid 120 for injecting the electrolyte into the container 100 .
  • the liquid injection stopper 132 is a member that closes the liquid injection port 131. Specifically, the liquid injection stopper 132 is joined to the lid body 120 after the inside of the container 100 is evacuated from the liquid injection port 131 and the electrolyte is injected into the inside of the container 100 during manufacturing of the power storage element 10. This is a closing member (lid member) that closes the liquid injection port 131.
  • the material of the liquid injection stopper 132 is not particularly limited, but any metal that can be used for the container 100 (lid 120) can be used. In particular, the liquid injection stopper 132 is preferably formed of a material that can be welded to the lid 120, such as the same material as the lid 120.
  • the terminal 300 is a terminal member (a positive terminal and a negative terminal) that is electrically connected to the electrode body 700 via the current collector 600.
  • the terminal 300 is used to lead the electricity stored in the electrode body 700 to the external space of the electricity storage element 10 and to introduce electricity into the internal space of the electricity storage element 10 in order to store electricity in the electrode body 700.
  • It is a metal member.
  • the terminal 300 is made of a conductive member such as metal such as aluminum, aluminum alloy, copper, or copper alloy.
  • the terminal 300 is connected (joined) to the current collector 600 and attached to the lid 120 by caulking, welding, or the like.
  • terminal 300 is arranged so as to protrude in the Z-axis positive direction from the outer surface (the surface in the Z-axis positive direction) of the lid body 120.
  • terminal 300 is a welding terminal that is joined to an external conductive member such as a bus bar by welding.
  • terminal 300 may also be a bolt terminal.
  • the bolt terminal has a bolt portion in which a male screw portion protruding in the positive direction of the Z-axis is formed, and is joined to the conductive member by bolt connection.
  • the current collector 600 is a conductive current collecting member (a positive electrode current collector and a negative electrode current collector) that is connected (joined) to the electrode body 700 and the terminal 300 and electrically connects the electrode body 700 and the terminal 300. ).
  • current collectors 600 are arranged on both sides of electrode body 700 in the X-axis direction.
  • the current collector 600 and an end 720 of an electrode body 700, which will be described later, are connected (joined) by welding, caulking, or the like. Further, as described above, the current collector 600 and the terminal 300 are connected (joined) by caulking, welding, or the like, and are fixed to the lid 120.
  • the positive electrode current collector 600 is formed of aluminum or an aluminum alloy, etc., like the positive electrode current collector foil 741 of the electrode body 700, which will be described later.
  • the current collector 600 is made of copper, copper alloy, or the like, like the negative electrode current collector foil 751 of the electrode body 700 described later.
  • the upper gasket 400 is a plate-shaped and rectangular insulating member that is disposed between the lid 120 of the container 100 and the terminal 300, and insulates and seals between the lid 120 and the terminal 300.
  • the lower gasket 500 is a plate-shaped and rectangular insulating member that is disposed between the lid 120 and the current collector 600 and insulates between the lid 120 and the current collector 600.
  • the upper gasket 400 and the lower gasket 500 are made of polypropylene (PP), polyethylene (PE), polystyrene (PS), polyphenylene sulfide resin (PPS), polyphenylene ether (PPE (including modified PPE)), polyethylene terephthalate (PET), Polybutylene terephthalate (PBT), polyether ether ketone (PEEK), tetrafluoroethylene perfluoroalkyl vinyl ether (PFA), polytetrafluoroethylene (PTFE), polyether sulfone (PES), polyamide (PA), ABS resin , or an insulating member such as a composite material thereof.
  • PP polypropylene
  • PE polyethylene
  • PS polystyrene
  • PPS polyphenylene sulfide resin
  • PPE polyphenylene ether
  • PET polyethylene terephthalate
  • PBT Polybutylene terephthalate
  • PEEK polyether ether ketone
  • the electrode body 700 is a power storage element (power generation element) that is formed by laminating electrode plates and separators and is capable of storing electricity.
  • the electrode body 700 is formed by winding an electrode plate and a separator.
  • the electrode body 700 has an elongated shape extending in the X-axis direction, and has an oval shape (long columnar shape) when viewed from the X-axis direction.
  • the electrode body 700 has an electrode body body part 710 and an end part 720 protruding from the electrode body body part 710 on both sides in the X-axis direction, and as described above, the end part 720 is connected (joined) to the current collector 600. ) to be done.
  • a through hole 730 is formed in the electrode main body portion 710. The configuration of such an electrode body 700 will be described in detail below.
  • FIG. 3 is a perspective view showing the configuration of an electrode body 700 according to this embodiment.
  • FIG. 3 shows the structure of the electrode body 700 in a partially unfolded state in which the electrode plates are wound.
  • FIG. 4 is a perspective view and a cross-sectional view showing the configuration of an electrode body 700 according to this embodiment.
  • FIG. 4(a) is a perspective view showing the configuration of the electrode body 700 after winding the electrode plate, and
  • FIG. 4(b) is an enlarged cross-section of a part of the electrode body 700.
  • FIG. 4(a) is a perspective view showing the configuration of the electrode body 700 after winding the electrode plate
  • FIG. 4(b) is an enlarged cross-section of a part of the electrode body 700.
  • the electrode body 700 has two electrode plates, a positive electrode plate 740 and a negative electrode plate 750, and has two separators 760 as separators. 761 and 762.
  • the positive electrode plate 740 is an electrode plate (electrode plate) in which a positive electrode active material layer 742 is formed on the surface of a positive electrode current collector foil 741 that is a long strip-shaped current collector foil (metal foil) made of metal such as aluminum or aluminum alloy.
  • the negative electrode plate 750 is an electrode plate (electrode plate) in which a negative electrode active material layer 752 is formed on the surface of a negative electrode current collector foil 751, which is a long strip-shaped current collector foil (metal foil) made of metal such as copper or copper alloy. ).
  • the positive electrode current collector foil 741 and the negative electrode current collector foil 751 materials such as nickel, iron, stainless steel, titanium, fired carbon, conductive polymer, conductive glass, Al-Cd alloy, etc., can be used to prevent oxidation-reduction reactions during charging and discharging. Any known material may be used as long as it is stable.
  • the positive electrode active material used in the positive electrode active material layer 742 and the negative electrode active material used in the negative electrode active material layer 752 any known material can be used as long as it is a positive electrode active material and a negative electrode active material that can intercalate and extract lithium ions. can be used.
  • polyanion compounds such as LiMPO 4 , LiMSiO 4 , LiMBO 3 (M is one or more transition metal elements selected from Fe, Ni, Mn, Co, etc.), lithium titanate, LiMn 2 Spinel-type lithium manganese oxide such as O 4 or LiMn 1.5 Ni 0.5 O 4 , LiMO 2 (M is one or more transition metal elements selected from Fe, Ni, Mn, Co, etc.) Lithium transition metal oxides such as the following can be used.
  • negative electrode active materials include lithium metal, lithium alloys (lithium metal-containing alloys such as lithium-silicon, lithium-aluminum, lithium-lead, lithium-tin, lithium-aluminum-tin, lithium-gallium, and Wood alloys). , alloys that can absorb and release lithium, carbon materials (graphite, non-graphitizable carbon, easily graphitizable carbon, low-temperature firing carbon, amorphous carbon, etc.), silicon oxides, metal oxides, lithium metal oxides (Li 4 Ti 5 O 12 etc.), polyphosphoric acid compounds, or compounds of transition metals and Group 14 to Group 16 elements, such as Co 3 O 4 or Fe 2 P, which are generally called conversion negative electrodes.
  • lithium metal lithium alloys
  • lithium metal-containing alloys such as lithium-silicon, lithium-aluminum, lithium-lead, lithium-tin, lithium-aluminum-tin, lithium-gallium, and Wood alloys.
  • alloys that can absorb and release lithium include carbon materials (
  • the separator 760 (separators 761 and 762) includes a separator base material 760a and an inorganic coat layer 760b containing inorganic particles coated on the separator base material 760a (see (b) in FIG. 4).
  • the separator base material 760a is a base material of the separator 760, and is a microporous insulating sheet made of resin or the like.
  • any known material can be used as appropriate, as long as it does not impair the performance of power storage element 10. Examples of the shape of the separator base material 760a include woven fabric, nonwoven fabric, and porous resin film.
  • a porous resin film is preferred from the viewpoint of strength, and a nonwoven fabric is preferred from the viewpoint of electrolyte retention.
  • a material for the separator base material 760a polyolefins such as polyethylene and polypropylene are preferred from the viewpoint of a shutdown function, and polyimide, aramid, etc. are preferred from the viewpoint of oxidative decomposition resistance.
  • a composite material of these resins may be used as the separator base material 760a.
  • the inorganic coat layer 760b is a coat layer that is coated on the separator base material 760a.
  • the inorganic coat layer 760b includes inorganic particles and a binder (binding material), and is coated on the separator base material 760a with the binder.
  • the binder any known material can be used as appropriate.
  • the inorganic coating layer 760b is a thin film-like portion that is thinner than the separator base material 760a and covers the entire surface (one side) of the separator base material 760a.
  • the inorganic coat layer 760b is not limited to covering the entire surface of the separator base material 760a, and may not cover a part of the surface. In FIG.
  • the inorganic coat layer 760b covers the surface of the separator base material 760a in the Y-axis negative direction, but it may cover the surface of the separator base material 760a in the Y-axis positive direction, or Both sides of 760a may be covered.
  • the inorganic coat layer 760b may be thicker than the separator base material 760a. However, it is preferable that the inorganic coating layer 760b covers one side of the separator base material 760a and is thinner than the separator base material 760a because the thickness of the separator 760 can be reduced.
  • the inorganic coating layer 760b coated on the separator base material 760a has an electrolyte permeation area of 80 mm 2 or more at 300 seconds after the electrolyte is dropped.
  • Table 1 shows a comparison of the permeation area of the electrolytic solution at 300 seconds after the electrolytic solution was dropped in a separator having an organic coating layer and a separator having an inorganic coating layer.
  • the method for measuring the permeation area is as follows. The evaluation sample is placed on a glass plate so that the front side becomes the coating layer and the back side becomes the separator base material 760a, and 0.3 cc of electrolytic solution is dropped into the center of the sample.
  • the time when the electrolytic solution adheres to the organic or inorganic coating layer is defined as 0 seconds, and the area that changes color due to penetration of the solution at 300 seconds is considered to be the penetration range.
  • the electrolytic solution dropped onto the organic or inorganic coating layer spreads in a circular shape, the diameter of the permeation range is measured at three locations, and the area of the circle calculated from the average value of the diameters is defined as the permeation area. If the spread of the electrolyte is visually confirmed to be a distorted shape that is not circular, such as an ellipse, the area that has changed color due to penetration of the solution is considered the penetration range, and image processing is performed to calculate the penetration area. calculate.
  • PC propylene carbonate
  • inorganic substances such as aluminum silicate, barium sulfate, and alumina (boehmite) are The test was conducted using particles with a particle diameter of approximately 5 ⁇ m. The larger the particle size, the faster the penetration rate, so the average primary particle size of the inorganic substance (inorganic particles) is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more. The particle diameter of the inorganic substance (inorganic particles) is equal to or less than the thickness of the inorganic coat layer 760b.
  • the The permeation area of the electrolyte is 80 mm 2 or more.
  • the inorganic coat layer 760b contains inorganic particles such as aluminum silicate, barium sulfate, and alumina (boehmite), and the permeation area of the electrolyte at 300 seconds after the electrolyte is dropped is 80 mm. It is 2 or more. Since barium sulfate and alumina (boehmite) have a larger permeation area than aluminum silicate, the inorganic coat layer 760b preferably contains at least one of barium sulfate and alumina as inorganic particles. In this case, the inorganic coat layer 760b has an electrolytic solution permeation area of 90 mm 2 or more (95 mm 2 ) 300 seconds after the electrolytic solution is dropped.
  • the inorganic coat layer 760b may contain one type of these inorganic substances as inorganic particles, or may contain multiple types of inorganic substances.
  • the particle size of the inorganic particles is about 5 ⁇ m.
  • the electrode body 700 is formed by alternately stacking and winding the positive electrode plate 740 and the negative electrode plate 750 configured as described above, and the separators 761 and 762. That is, the electrode body 700 is formed by stacking a positive electrode plate 740, a separator 761, a flat negative electrode plate 750, and a separator 762 in this order and winding them (see FIG. 4B, etc.).
  • the electrode body 700 is a wound type electrode body, and is formed by winding a positive electrode plate 740, a negative electrode plate 750, etc. around a winding axis L extending in the X-axis direction.
  • the winding axis L is a virtual axis that becomes the central axis when winding the positive electrode plate 740, the negative electrode plate 750, etc. They are parallel straight lines.
  • the electrode body 700 includes a positive electrode plate 740 and a negative electrode plate 750 that is shifted from the positive electrode plate 740 in the direction along the winding axis L (the winding axis direction, in this embodiment, the X-axis direction). , are formed by laminating and then winding. Separator 761 and separator 762 are arranged to be interposed between positive electrode plate 740 and negative electrode plate 750 after winding.
  • the positive electrode active material layer 742 and the negative electrode active material layer 752 are not formed (coated) on the ends in the respective shifted directions, and the positive electrode current collector foil 741 and the negative electrode current collector foil 751 has an exposed portion (active material layer non-forming portion).
  • the electrode body 700 has a positive electrode end 720 in which the active material layer-free portion of the positive electrode plate 740 is laminated and bundled at one end in the winding axis direction, and the other end in the winding axis direction.
  • the active material layer-free portion of the negative electrode plate 750 is stacked and bundled to form a negative electrode end portion 720.
  • the end portion 720 is a portion where the positive electrode plate 740 or the negative electrode plate 750 are stacked in the stacking direction (Y-axis direction).
  • the electrode body 700 includes an electrode body body part 710 that constitutes the body of the electrode body 700, and a pair of end parts 720 (a positive electrode and a negative electrode) that protrude from the electrode body body part 710 on both sides in the X-axis direction.
  • the electrode main body portion 710 includes a portion of the positive electrode plate 740 on which the positive electrode active material layer 742 is formed (coated), and a portion of the negative electrode plate 750 on which the negative electrode active material layer 752 is formed (coated).
  • the electrode main body part 710 has a pair of curved parts 711 made up of parts on both sides in the Z-axis direction, and a pair of flat parts 712 made up of parts on both sides in the Y-axis direction ((a) in FIG. 4). reference). That is, the electrode body 700 has a curved portion 711 and a flat portion 712, which are formed by winding the positive electrode plate 740 and the negative electrode plate 750 around the winding axis L.
  • the curved portion 711 is a curved portion that is curved in a semicircular arc shape so as to protrude in the Z-axis direction when viewed from the X-axis direction, and extends in the X-axis direction, and is a curved portion that extends in the X-axis direction. It is arranged opposite to the body 120. That is, the pair of curved portions 711 are portions that are curved so as to protrude on both sides in the Z-axis direction toward the bottom wall portion 113 and the lid 120 of the container body 110 when viewed from the X-axis direction.
  • the flat portion 712 is a rectangular and flat portion that connects the ends of the pair of curved portions 711 and extends parallel to the XZ plane facing the Y-axis direction, and is a long side wall on both sides of the container body 110 in the Y-axis direction. It is arranged opposite to the section 111.
  • the curved shape of the curved portion 711 is not limited to a semicircular arc shape, but may be a part of an elliptical shape or the like, and may be curved in any manner.
  • the flat portion 712 is not limited to having a flat outer surface facing the Y-axis direction, and may be slightly recessed or slightly bulged.
  • the electrode body 700 has an elongated (horizontally elongated) shape with a long length in the X-axis direction.
  • the length of the electrode body 700 in the direction of the winding axis is 500 mm or more.
  • the length from one end edge to the other end edge of the electrode body 700 in the X-axis direction, which is the winding axis direction is 500 mm or more.
  • the length of the electrode body 700 in the direction of the winding axis is preferably longer than 500 mm, more preferably 550 mm or more, and even more preferably 600 mm or more.
  • the length from one end edge to the other end edge of the electrode main body portion 710 may be 500 mm or more, preferably longer than 500 mm, and preferably 550 mm or more. is more preferable, and even more preferably 600 mm or more.
  • one or more through holes 730 are formed in the electrode body 700. That is, one or more through holes 730 are formed in the electrode plates (positive electrode plate 740 and negative electrode plate 750) of the electrode body 700. In this embodiment, one through hole 730 is formed in the electrode body main body portion 710 of the electrode body 700. Below, the configuration of the through hole 730 will be explained in detail using FIG. 5 as well.
  • FIG. 5 is a front view and a cross-sectional view showing the configuration of the through hole 730 of the electrode body 700 according to the present embodiment.
  • 5(a) is a front view showing the configuration of the through hole 730 of the electrode body 700 when viewed from the front (Y-axis negative direction), and FIG. FIG.
  • the through hole 730 is formed at the center in the X-axis direction and at the end in the Z-axis minus direction of the flat portion 712 in the Y-axis minus direction of the electrode body 710.
  • the through hole 730 is disposed opposite to the long side wall 111 of the container body 110 of the container 100 in the negative Y-axis direction and close to the bottom wall 113 .
  • the portion of the positive electrode plate 740 where the positive electrode active material layer 742 is formed (coated) on the positive current collector foil 741 is referred to as a positive electrode active material portion 743.
  • a portion of the negative electrode plate 750 in which the negative electrode active material layer 752 is formed (coated) on the negative electrode current collector foil 751 is referred to as a negative electrode active material portion 753 .
  • the positive electrode current collector foil 741 and the positive electrode active material layer 742 excluding the portion included in the end portion 720 of the positive electrode are referred to as a positive electrode active material portion 743
  • the negative electrode collector foil 741 excluding the portion included in the end portion 720 of the negative electrode are referred to as a positive electrode active material portion 743
  • the electric foil 751 and the negative electrode active material layer 752 are referred to as a negative electrode active material portion 753.
  • the portion other than the positive electrode current collector foil 741 included in the positive electrode end 720 of the positive electrode plate 740 is referred to as the positive electrode active material portion 743
  • the negative electrode included in the negative electrode end 720 of the negative electrode plate 750 is referred to as the positive electrode active material portion 743
  • a portion other than the current collector foil 751 is referred to as a negative electrode active material portion 753.
  • positive electrode active material layers 742 are formed on both sides of a positive electrode current collector foil 741 (one layer) of the positive electrode plate 740 in the electrode body 700.
  • the three layers formed as one unit are referred to as one positive electrode active material portion 743.
  • the electrode main body part 710 is formed by laminating these plurality of positive electrode active material parts 743, plurality of negative electrode active material parts 753, and separators 761 and 762.
  • a through hole 730 is formed in at least one of the positive electrode active material portion 743 and the negative electrode active material portion 753 located on the flat portion 712 of the electrode main body portion 710.
  • through holes 730 are formed in both the positive electrode active material section 743 and the negative electrode active material section 753, as well as in the separators 761 and 762.
  • a positive electrode through hole 743a serving as the through hole 730 is formed in the positive electrode active material portion 743.
  • the positive electrode through hole 743a is a circular through hole that penetrates the positive electrode active material portion 743 in the Y-axis direction.
  • the positive electrode through hole 743a is a circular through hole that penetrates the positive electrode current collector foil 741 and the two positive electrode active material layers 742 provided on both sides of the positive electrode current collector foil 741 in the Y axis direction.
  • a negative electrode through hole 753 a serving as the through hole 730 is formed in the negative electrode active material portion 753 .
  • the negative electrode through hole 753a is a circular through hole that penetrates the negative electrode active material portion 753 in the Y-axis direction.
  • the negative electrode through hole 753a is a circular through hole that penetrates the negative electrode current collector foil 751 and the two negative electrode active material layers 752 provided on both sides of the negative electrode current collector foil 751 in the Y axis direction. be.
  • the positive electrode through hole 743a and the negative electrode through hole 753a are arranged at a position where at least a portion thereof overlaps when viewed from the penetrating direction of the through hole 730 (the direction in which the positive electrode through hole 743a and the negative electrode through hole 753a are lined up, the Y-axis direction).
  • the negative electrode through hole 753a when viewed from the Y-axis direction, is arranged at a position where the entire negative electrode through hole 743a overlaps with the positive electrode through hole 743a. That is, when viewed from the Y-axis direction, the negative electrode through hole 753a has a smaller shape than the positive electrode through hole 743a, and is arranged inside the positive electrode through hole 743a.
  • the positive electrode through hole 743a and the negative electrode through hole 753a are smaller, from the viewpoint of suppressing a decrease in the capacity of the electricity storage element 10.
  • the size is not too small, as it will be difficult to remove the electrode plate.
  • the positive electrode through hole 743a and the negative electrode through hole 753a (through hole 730) preferably have a diameter of 0.8 mm or more (opening area of 0.5 mm 2 or more), and a diameter of 1 mm or more (opening area of 0.5 mm 2 or more). is more preferably 0.785 mm 2 or more).
  • the negative electrode through hole 753a is a circular through hole with a diameter of about 0.8 mm to 3 mm, and the positive electrode through hole 743a has a diameter of about 1.5 mm to 5 mm. It is a circular through hole. That is, all the positive electrode through holes 743a and the negative electrode through holes 753a (through holes 730) have an opening area of 0.5 mm 2 or more (diameter of 0.8 mm or more).
  • the positive electrode through hole 743a and the negative electrode through hole 753a can be formed by laser processing (laser welding, laser cutting), etc. before winding the positive electrode plate 740 and the negative electrode plate 750.
  • the positive electrode through holes 743a may be formed by forming (coating) the positive electrode active material layer 742 on the positive electrode current collector foil 741 in which through holes are formed in advance, or by forming the positive electrode active material layer 742 on the positive electrode current collector foil 741.
  • the positive electrode through hole 743a may be formed by punching out the positive electrode current collector foil 741 and the positive electrode active material layer 742 after forming (coating). The same applies to the negative electrode through hole 753a.
  • the positive electrode through hole 743a and the negative electrode through hole 753a can be formed by press working, it is preferable to form them by laser working in order to process small holes at high speed.
  • the plurality of positive electrode active material parts 743 and the plurality of negative electrode active material parts 753 are stacked in the stacking direction.
  • the plurality of positive electrode active material parts 743 and the plurality of negative electrode active material parts 753 are stacked in a direction perpendicular to the flat surface of the flat part 712 (that is, in the Y-axis direction).
  • a plurality of positive electrode through holes 743a and a plurality of negative electrode through holes 753a are formed in the plurality of positive electrode active material parts 743 and the plurality of negative electrode active material parts 753, which are arranged continuously in the stacking direction.
  • a plurality of positive electrode through holes 743a and a plurality of negative electrode through holes 753a as the through holes 730 are formed in the positive electrode plate 740 and the negative electrode plate 750, respectively.
  • the plurality of positive electrode through holes 743a and the plurality of negative electrode through holes 753a are arranged at overlapping positions when viewed from the penetrating direction of the through hole 730.
  • the penetrating direction of the through holes 730 (the plurality of positive electrode through holes 743a and the plurality of negative electrode through holes 753a) can be defined as the Y-axis direction.
  • the plurality of positive electrode through holes 743a are formed from the positive electrode active material portion 743 located at the innermost layer (innermost circumference) in the electrode body 700 to the outermost layer (the outermost layer) so that the positive electrode plate 740 and the negative electrode plate 750 are aligned after being wound.
  • the intervals are formed such that the distance increases toward the positive electrode active material portion 743 located at the outer periphery. The same applies to the negative electrode through hole 753a.
  • the through-hole 730 is also formed in the active material portion disposed in the outermost layer (outermost periphery) of the plurality of positive electrode active material portions 743 and the plurality of negative electrode active material portions 753.
  • the negative electrode active material portion 753 is arranged in the outermost layer (outermost periphery) of the electrode body 700
  • the negative electrode through hole 753a is also formed in the outermost negative electrode active material portion 753.
  • the plurality of positive electrode through holes 743a and the plurality of negative electrode through holes 753a extend from the active material part of the outermost layer (outermost periphery) to the active material part of the innermost layer (innermost periphery) in the electrode body 700. Formed continuously.
  • all the negative electrode through holes 753a formed in the plurality of negative electrode active material parts 753 are arranged inside all the positive electrode through holes 743a formed in the plurality of positive electrode active material parts 743. be done.
  • a separator through hole 761a as the through hole 730 is formed in the separator 761 (separator base material 760a and inorganic coat layer 760b).
  • the separator through hole 761a is a circular through hole that penetrates the separator 761 in the Y-axis direction.
  • a separator through hole 762a as the through hole 730 is formed in the separator 762 (separator base material 760a and inorganic coat layer 760b).
  • the separator through hole 762a is a circular through hole that penetrates the separator 762 in the Y-axis direction.
  • the separator through holes 761a and 762a have the same shape and the same size, but they may have different shapes or different sizes.
  • Separator through-holes 761a and 762a are at least partially connected to positive electrode through-hole 743a and negative electrode through-hole 753a when viewed from the through-hole direction of through-hole 730 (line direction of positive electrode through-hole 743a and negative electrode through-hole 753a, Y-axis direction). placed in overlapping positions.
  • separator through holes 761a and 762a are arranged at positions where all of them overlap with positive electrode through hole 743a and partially overlap with negative electrode through hole 753a, when viewed from the Y-axis direction.
  • the separator through holes 761a and 762a when viewed from the Y-axis direction, have a shape smaller than the positive electrode through hole 743a and larger than the negative electrode through hole 753a, and are arranged inside the positive electrode through hole 743a. Moreover, the negative electrode through hole 753a is arranged inward.
  • the separator through holes 761a and 762a are circular through holes with a diameter of approximately 1 mm to 4 mm.
  • the separator through holes 761a and 762a can be formed by laser processing, press processing, etc. before winding the positive electrode plate 740 and the negative electrode plate 750, similarly to the positive electrode through hole 743a and the negative electrode through hole 753a.
  • the separator through holes 761a and 762a may be processed by irradiating the positions of the positive electrode through hole 743a and the negative electrode through hole 753a with a laser after winding the positive electrode plate 740 and the negative electrode plate 750.
  • the separator through holes 761a and 762a may be the same size as the negative electrode through hole 753a, or may be smaller in size than the negative electrode through hole 753a.
  • a plurality of separator through-holes 761a and 762a are formed continuously in the Y-axis direction in the separators 761 and 762 along with a plurality of positive electrode through-holes 743a and a plurality of negative electrode through-holes 753a. That is, a plurality of separator through holes 761a and 762a are continuous from the separator 761 or 762 located at the outermost layer (outermost periphery) to the separator 761 or 762 located at the innermost layer (innermost periphery) in the electrode body 700. It is formed by As a result, in the electrode body 700, all separator through holes 761a and 762a formed in separators 761 and 762 are arranged inside all positive electrode through holes 743a when viewed from the Y-axis direction.
  • “number of through holes” is the number (presence or absence) of through holes 730 formed in the electrode body 700 shown in FIG. In Examples 7 to 6, no through hole 730 was formed, and in Examples 7 and 8, one through hole 730 was formed in the electrode body 700.
  • the "length of the electrode body” is the length from one end edge to the other edge of the electrode body 700 in the X-axis direction (winding axis direction), and is 300 mm in Reference Example 1, Comparative Examples 1 and 2, and Example In Examples 1 to 3, it was 500 mm, and in Examples 4 to 8, it was 600 mm.
  • Presence or absence of coat layer refers to whether or not the separator 760 is provided with a coat layer.
  • the separator 760 is not provided with a coat layer, and in Comparative Example 2 and Example In Nos. 1 to 8, the separator 760 was provided with a coating layer.
  • “Type of coating layer” is the type of coating layer provided on the separator 760, and includes aramid fiber in Comparative Example 2, aluminum silicate in Examples 1 and 4, barium sulfate in Examples 2, 5, and 7, and barium sulfate in Examples 2, 5, and 7. In Examples 3, 6, and 8, it was alumina (boehmite).
  • the permeation area column, the values of the permeation area corresponding to the types of coating layers shown in Table 1 are listed again.
  • the "Liquid Penetration Time” column shows the experimental results of the time required for the electrolytic solution to penetrate into the entire electrode body 700 after dropping the electrolytic solution onto the target electrode body 700.
  • Table 2 in all cases of Reference Example 1, Comparative Examples 1 and 2, and Examples 1 to 8, the width of the electrode body 700 (length in the Z-axis direction) is 135.6 mm, and the width of the electrode body 700 is 135.6 mm.
  • the thickness (length in the Y-axis direction) was 19.4 mm.
  • the diameter of the negative electrode through-hole 753a was 1 mm
  • the diameter of the positive electrode through-hole 743a was 3 mm
  • the diameter of separator through-holes 761a and 762a was 2 mm.
  • the electrode body 700 can be formed in a relatively short time (within 2 hours). The electrolyte penetrates. However, as shown in Comparative Example 1, when the separator 760 is not provided with a coating layer and the length of the electrode body 700 is 500 mm, the electrode body 700 is electrolyzed even after a long period of time (6 hours). Liquid does not penetrate.
  • an inorganic coating layer 760b (aluminum silicate, barium sulfate, or alumina (boehmite)) containing an inorganic substance (inorganic particles) is provided on the separator 760, as shown in Examples 1 to 3,
  • the electrolytic solution permeates into the electrode body 700 in a short period of time (within 2 hours). Therefore, it can be seen that when the length of the electrode body 700 is 500 mm or more, it is necessary to provide the inorganic coating layer 760b on the separator 760. It is preferable that the inorganic coat layer 760b has an electrolytic solution permeation area of 80 mm 2 or more at 300 seconds after the electrolytic solution is dropped.
  • Comparative Examples 1 and 2 and Examples 1 to 3 similar results are obtained even when the length of the electrode main body portion 710 (the length from one end edge to the other end edge in the X-axis direction) is 500 mm.
  • the inorganic coat layer 760b when the length of the electrode body 700 is 600 mm, when the inorganic coat layer 760b contains aluminum silicate as inorganic particles, the time for the electrolyte to penetrate into the electrode body 700 is slightly longer (4 (within hours).
  • the inorganic coating layer 760b when the inorganic coating layer 760b contains barium sulfate or alumina (boehmite) as inorganic particles, the The electrolytic solution permeates into the electrode body 700 in a short time (within 2 hours). Therefore, the inorganic coat layer 760b preferably contains at least one of barium sulfate and alumina as inorganic particles.
  • the inorganic coat layer 760b preferably has an electrolytic solution permeation area of 90 mm 2 or more (95 mm 2 ) 300 seconds after the electrolytic solution is dropped.
  • an electrolytic solution permeation area of 90 mm 2 or more (95 mm 2 ) 300 seconds after the electrolytic solution is dropped.
  • similar results can be obtained even when the length of the electrode main body portion 710 (the length from one end edge to the other end edge in the X-axis direction) is 600 mm.
  • the length of the electrode body 700 is 500 mm or more, preferably longer than 500 mm, more preferably 550 mm or more, and even more preferably 600 mm or more.
  • the length of the electrode main body portion 710 may be 500 mm or more, preferably longer than 500 mm, more preferably 550 mm or more, and even more preferably 600 mm or more.
  • the length of the electrode body 700 (or the length of the electrode body body part 710) is 800 mm.
  • the length is preferably 700 mm or less, and more preferably 700 mm or less.
  • the length of the electrode body 700 (or the length of the electrode body main body portion 710) is preferably 1600 mm or less, and more preferably 1400 mm or less.
  • the length of the electrode body 700 is preferably 500 mm or more and 800 mm or less, and less than 500 mm.
  • the length is more preferably 800 mm or less, further preferably 550 mm or more and 700 mm or less, and particularly preferably 600 mm or more and 700 mm or less.
  • the length of the electrode body 700 (or the length of the electrode body part 710) is preferably 500 mm or more and 1600 mm or less, and is preferably longer than 500 mm and 1600 mm. It is more preferably the following, further preferably 550 mm or more and 1400 mm or less, particularly preferably 600 mm or more and 1400 mm or less.
  • the power storage element 10 includes the wound electrode body 700, and the wall portion (lid body 120) extending in the direction of the winding axis of the electrode body 700 of the container 100.
  • An electrolyte injection part 130 is provided at . Therefore, when pouring the electrolyte into the container 100, the electrolyte is difficult to penetrate from the outside to the inside of the electrode body 700, making it difficult to infiltrate the electrolyte into the electrode body 700.
  • the separator 760 is coated with an inorganic coating layer 760b.
  • the permeability (liquid wettability and capillary force) of the electrolytic solution into the separator 760 can be improved. Therefore, the time for the electrolytic solution to penetrate into the electrode body 700 can be shortened, so that the electrolytic solution can easily penetrate into the electrode body 700. If the electrolytic solution penetrates into the electrode body 700 for a long time, there is a concern that the copper of the negative electrode plate 750 will be eluted and a short circuit will occur. The occurrence can be suppressed.
  • the inorganic coating layer 760b coated on the separator 760 is an inorganic inorganic material that allows the electrolyte to penetrate a relatively wide area in a relatively short period of time. This is a coat layer 760b. In this way, by using the inorganic coating layer 760b that allows the electrolyte to permeate into a relatively wide area in a relatively short time, the permeability of the electrolyte into the separator 760 can be improved. If it takes more than 6 hours for the electrolyte to penetrate into the electrode body 700, there is a concern that the copper of the negative electrode plate 750 will be eluted and a short circuit will occur. Since we obtained experimental results that allow penetration, the occurrence of the short circuit can be suppressed.
  • the inventor of the present application has discovered that when an electrolytic solution is dropped onto an inorganic coat layer 760b containing at least one of barium sulfate and alumina, the electrolytic solution is removed in a relatively short time compared to other inorganic particles (such as aluminum silicate). It has been found that it can penetrate into a relatively wide area of the inorganic coat layer 760b. When the inorganic coating layer 760b was used, an experimental result was obtained in which the electrolytic solution could penetrate into the electrode body 700 within 2 hours. Therefore, by including at least one of barium sulfate and alumina in the inorganic coating layer 760b coated on the separator 760, the permeability of the electrolyte into the separator 760 can be improved.
  • the inventor of the present invention has found that even when the electrode body 700 is used, the electrolytic solution can be easily penetrated into the electrode body 700 by coating the separator 760 with the inorganic coating layer 760b. Therefore, when such a long electrode body 700 is used, the effect of adopting the configuration of the present application is high.
  • the longer the length of the electrode body 700 the higher the effect of adopting the configuration of the present application, so the length of the electrode body 700 is 500 mm or more, preferably longer than 500 mm, and 550 mm or more. More preferably, the length is 600 mm or more.
  • the electrolyte can permeate into the electrode body 700 through the through-hole 730 from the separator 760 whose permeability for the electrolyte has been improved by the inorganic coating layer 760b.
  • the through hole 730 can be placed close to the bottom wall 113 of the container 100, so that the electrolytic solution collected at the bottom of the container 100 can permeate into the electrode body 700. Easy to do. In particular, even when the amount of electrolytic solution in container 100 is small (such as when the container is at the end of its life), the electrolytic solution accumulated in the lower part of container 100 can be permeated into electrode body 700.
  • the electrolytic solution can be stored in the through hole 730, so that the electrolytic solution is not consumed due to reduction of the electrolytic solution (SEI film formation) during charging and discharging. This can prevent the electrolyte from running out.
  • the gas is discharged from the gas discharge valve 140 to the outside of the power storage element 10 , the gas inside the electrode body 700 can be easily discharged through the through hole 730 .
  • the through hole 730 By forming the through hole 730 in the flat portion 712 of the electrode body main body portion 710 of the electrode body 700, the through hole 730 can be easily formed.
  • FIG. 6 is a front view and a cross-sectional view showing the configuration of a through hole 730 of an electrode body 700 according to Modification 1 of the present embodiment.
  • FIG. 6 is a diagram corresponding to FIG. 5.
  • the positive electrode through hole 743a is formed to have the same size as the negative electrode through hole 753a when viewed from the Y-axis direction, and the positive electrode active material layer 742 around the positive electrode through hole 743a
  • An insulating section 744 is provided in the. That is, the positive electrode plate 740 has an insulating part 744 that is arranged around the positive electrode through hole 743a and has an outer periphery 744a larger in size than the negative electrode through hole 753a.
  • the insulating portion 744 is a portion masked by melting an insulating member such as resin into the positive electrode active material layer 742 around the positive electrode through hole 743a.
  • the insulating portion 744 is a portion having a higher content of an insulating material such as resin than other portions of the positive electrode active material layer 742.
  • the insulating portion 744 can be formed by dissolving a UV-curable epoxy resin that is cured by irradiation with ultraviolet rays into the positive electrode active material layer 742, or by dissolving a polyolefin resin such as PE or PP melted by heating. .
  • the insulating portion 744 can be easily formed by pressing a resin molding die and pouring the resin.
  • the insulating part 744 is made of a binder-modified polyolefin sheet (a sheet member in which polar groups are introduced into polyolefin to give it adhesive properties with different materials) that has been previously formed into a shape that covers the periphery of the positive electrode through hole 743a. It may be placed in the positive electrode active material layer 742 around the electrode 743a, heated, melted, and impregnated. When the insulating material such as the resin permeates into the positive electrode active material layer 742, the positive electrode active material layer 742 is deactivated (discharge capacity becomes smaller).
  • a binder-modified polyolefin sheet a sheet member in which polar groups are introduced into polyolefin to give it adhesive properties with different materials
  • the power storage element 10 can achieve the same effects as the above embodiment.
  • the negative electrode active material layer 752 is made of positive electrode active material regardless of the size of the positive electrode through hole 743a and the negative electrode through hole 753a.
  • the structure covers layer 742.
  • an insulating part 744 having an outer periphery 744a larger in size than the negative electrode through hole 753a is arranged around the positive electrode through hole 743a in the positive electrode plate 740.
  • the negative electrode active material layer 752 covers the positive electrode active material layer 742. be able to. In other words, by deactivating the positive electrode active material layer 742 around the positive electrode through hole 743a, the active positive electrode active material layer 742 can be covered with the negative electrode active material layer 752, and lithium electrodeposition onto the negative electrode plate 750 is suppressed. can.
  • the positive electrode through hole 743a may be smaller or larger than the negative electrode through hole 753a when viewed from the Y-axis direction, and the size of the outer periphery 744a of the insulating portion 744 may be larger than the negative electrode through hole 753a.
  • the separator through holes 761a and 762a may have the same size as the negative electrode through hole 753a and the positive electrode through hole 743a, or may have a smaller size than the negative electrode through hole 753a and the positive electrode through hole 743a.
  • the liquid injection part 130 is arranged on the lid 120 of the container 100, but it may be arranged on the container main body 110.
  • the liquid injection part 130 may be arranged on the long side wall part 111 of the container main body 110, or may be arranged on the bottom wall part 113.
  • the liquid injection part 130 may be disposed on a wall extending in the direction of the winding axis of the electrode body 700.
  • the gas exhaust valve 140 is arranged on the lid 120, it may be arranged on any wall of the container body 110.
  • inorganic particles contained in the inorganic coat layer 760b of the separator 760 are exemplified as inorganic particles contained in the inorganic coat layer 760b of the separator 760, but the inorganic particles are not limited thereto.
  • the inorganic coat layer 760b may contain any inorganic particles as long as the time for the electrolyte to penetrate into the electrode body 700 can be shortened.
  • the inorganic coat layer 760b of the separator 760 has an electrolyte permeation area of 80 mm 2 or more at 300 seconds after the electrolyte is dropped, but the invention is not limited to this.
  • the permeation area may be smaller than 80 mm 2 as long as the time for permeation of the electrolyte into the electrode body 700 can be shortened.
  • separators 761 and 762 may be made of the same material or may be made of different materials. That is, the separator base material 760a of the separator 761 and the separator base material 760a of the separator 762 may be formed of the same material or may be formed of different materials.
  • the inorganic coat layer 760b of the separator 761 and the inorganic coat layer 760b of the separator 762 may contain the same inorganic particles or may contain different inorganic particles.
  • the through hole 730 of the electrode body 700 is formed at the center in the X-axis direction and at the end in the negative Z-axis direction of the flat portion 712 in the Y-axis minus direction of the electrode body body 710. , may be formed at any position on the electrode body 700.
  • the through hole 730 may be formed at the end of the flat portion 712 in the X-axis direction, the center in the Z-axis direction, or the end in the positive Z-axis direction.
  • the through hole 730 may be formed in the flat portion 712 of the electrode body portion 710 in the positive Y-axis direction, or may be formed in the curved portion 711 of the electrode body portion 710. When the through hole 730 is formed in the curved portion 711, the through hole 730 is less likely to be blocked by the container 100, making it easier for the electrolyte to penetrate into the electrode body 700.
  • one through hole 730 is formed in the electrode body 700, but two or more through holes 730 may be formed.
  • the arrangement position of the through-hole 730 is not particularly limited, but if the length of the electrode body 700 in the X-axis direction becomes longer, a plurality of through-holes 730 are formed at different positions in the X-axis direction of the electrode body 700. is preferable.
  • the length of the electrode body 700 in the Z-axis direction becomes long, it is preferable to form a plurality of through holes 730 at different positions in the Z-axis direction of the electrode body 700. These allow the electrolytic solution to easily penetrate into the electrode body 700.
  • the effective electrode area of the electrode body 700 is the area of the region in the electrode plate where the active material layer is arranged (specifically, the region in the positive electrode plate 740 where the positive electrode active material layer 742 is arranged).
  • the rate at which this effective electrode area is reduced is referred to as the opening area ratio.
  • the opening area ratio is the ratio of the total opening area of one or more through holes 730 located within the region to the area of the region in the electrode plate where the active material layer is arranged.
  • the opening area ratio is the ratio of the total opening area of the positive electrode through holes 743a located within the region to the area of the region in the positive electrode plate 740 where the positive electrode active material layer 742 is arranged.
  • the opening area ratio is the ratio of the total opening area of the positive electrode through holes 743a located in the region where the positive electrode active material layer 742 is disposed to the area of the region when the wound state of the electrode body 700 is unfolded to spread the positive electrode plate 740 and the positive electrode plate 740 is viewed in a plan view.
  • the opening area ratio is preferably 3% or less, and more than 0.1%, from the viewpoint of suppressing a decrease in the capacity of the power storage element 10. It is more preferably small, and even more preferably smaller than 0.05%. As described above, the opening area ratio can also be said to be the ratio of the amount of capacity reduction (capacity loss) of the power storage element 10 due to the through hole 730. Therefore, the rate of capacity reduction (capacity loss) of the electricity storage element 10 is also preferably 3% or less, more preferably less than 0.1%, and even more preferably less than 0.05%. .
  • the through holes 730 are formed in all of the plurality of stacked positive electrode active material parts 743 and the plurality of negative electrode active material parts 753. , but not limited to.
  • the through hole 730 may not be formed in any of the positive electrode active material portions 743 or any of the negative electrode active material portions 753.
  • the separators 761 and 762 the portions where the through holes 730 (separator through holes 761a and 762a) are not formed between the outermost layer separators 761 and 762 and the innermost layer separators 761 and 762 in the electrode body 700 There may be.
  • the through holes 730 are formed in both the positive electrode active material portion 743 and the negative electrode active material portion 753, but the present invention is not limited thereto.
  • the through hole 730 may be formed only in either one of the positive electrode active material portion 743 and the negative electrode active material portion 753.
  • the through hole 730 (separator through holes 761a, 762a) may be formed only in either one of the separators 761 and 762, or the through hole 730 may be formed in both the separators 761 and 762. It does not have to be formed.
  • a structure in which the through hole 730 is not formed in the electrode body 700 may also be used.
  • the negative electrode through hole 753a has a smaller shape than the positive electrode through hole 743a when viewed from the Y-axis direction, and is arranged inside the positive electrode through hole 743a. is not limited to.
  • the negative electrode through hole 753a may not be placed inside the positive electrode through hole 743a, but may be placed at a position slightly shifted from the positive electrode through hole 743a, or may be placed at a position that does not overlap with the positive electrode through hole 743a.
  • the shape, size relationship, and arrangement position of the negative electrode through hole 753a are not particularly limited.
  • separator through holes 761a and 762a may be arranged at positions slightly shifted from positive electrode through holes 743a and negative electrode through holes 753a, or may be arranged at positions that do not overlap with positive electrode through holes 743a and negative electrode through holes 753a. You can.
  • the shape, size relationship, and arrangement position of the separator through holes 761a and 762a, the positive electrode through hole 743a, and the negative electrode through hole 753a are not particularly limited. However, even in this case, it is preferable that all of the positive electrode active material layer 742 (active positive electrode active material layer 742) face the separators 761 and 762.
  • both of the pair of terminals 300 are arranged to protrude from the container 100 in the positive Z-axis direction, but the direction in which the terminals 300 protrude is not particularly limited.
  • the pair of terminals 300 may protrude from the container 100 in either one of the X-axis directions, or may protrude in both X-axis directions.
  • the electrode body 700 has an elongated cylindrical shape (flat shape) having a curved part 711 and a flat part 712, but it may also have a cylindrical shape, an elliptical cylindrical shape, etc., or a wound type electrode body. If so, its shape is not particularly limited.
  • the end portion 720 may be a tab portion (a portion where a plurality of tabs of the electrode plate are stacked) projecting from a part of the electrode body main body portion 710.
  • the electrode body 700 does not have to have a long shape in the X-axis direction.
  • the present invention can be applied to power storage elements such as lithium ion secondary batteries.

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Abstract

La présente invention concerne un élément de stockage d'énergie qui est pourvu : d'un corps d'électrode qui est obtenu par enroulement d'une plaque d'électrode et d'un séparateur ; d'une solution d'électrolyte ; et d'un récipient dans lequel le corps d'électrode et la solution d'électrolyte sont contenus. Le récipient présente une partie d'injection de liquide pour la solution d'électrolyte sur une partie de paroi qui s'étend dans la direction de l'axe d'enroulement du corps d'électrode ; le corps d'électrode présente une longueur égale ou supérieure à 500 mm dans la direction de l'axe d'enroulement ; et le séparateur comprend un matériau de base de séparateur et une couche de revêtement inorganique qui contient des particules inorganiques et qui est revêtue sur le matériau de base de séparateur.
PCT/JP2023/027085 2022-09-16 2023-07-25 Élément de stockage d'énergie WO2024057726A1 (fr)

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JP2022-148544 2022-09-16

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013118057A (ja) * 2011-12-01 2013-06-13 Gs Yuasa Corp セパレータ及びこれを用いた非水電解質二次電池
JP2015103420A (ja) * 2013-11-26 2015-06-04 日立オートモティブシステムズ株式会社 角形二次電池
JP2016213133A (ja) * 2015-05-13 2016-12-15 トヨタ自動車株式会社 非水電解液二次電池
WO2022163616A1 (fr) * 2021-01-29 2022-08-04 株式会社Ｇｓユアサ Élément de stockage d'électricité et dispositif de stockage d'électricité
WO2022168591A1 (fr) * 2021-02-03 2022-08-11 日本ゼオン株式会社 Composition de suspension pour couche résistante à la chaleur de batterie secondaire non aqueuse, couche résistante à la chaleur de batterie secondaire non aqueuse, séparateur avec couche résistante à la chaleur de batterie secondaire non aqueuse, et batterie secondaire non aqueuse

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013118057A (ja) * 2011-12-01 2013-06-13 Gs Yuasa Corp セパレータ及びこれを用いた非水電解質二次電池
JP2015103420A (ja) * 2013-11-26 2015-06-04 日立オートモティブシステムズ株式会社 角形二次電池
JP2016213133A (ja) * 2015-05-13 2016-12-15 トヨタ自動車株式会社 非水電解液二次電池
WO2022163616A1 (fr) * 2021-01-29 2022-08-04 株式会社Ｇｓユアサ Élément de stockage d'électricité et dispositif de stockage d'électricité
WO2022168591A1 (fr) * 2021-02-03 2022-08-11 日本ゼオン株式会社 Composition de suspension pour couche résistante à la chaleur de batterie secondaire non aqueuse, couche résistante à la chaleur de batterie secondaire non aqueuse, séparateur avec couche résistante à la chaleur de batterie secondaire non aqueuse, et batterie secondaire non aqueuse

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