Classifications

• • 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
  • H01G11/74—Terminals, e.g. extensions of current collectors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/543—Terminals
  • H01M50/552—Terminals characterised by their shape
  • H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • 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
  • 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
  • H01G11/80—Gaskets; Sealings
• • 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
  • H01G11/82—Fixing or assembling a capacitive element in a housing, e.g. mounting electrodes, current collectors or terminals in containers or encapsulations
• • 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
  • H01M50/105—Pouches or flexible bags
• • 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
  • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
• • 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
  • H01M50/147—Lids or covers
  • H01M50/148—Lids or covers characterised by their shape
  • H01M50/15—Lids or covers characterised by their shape for prismatic or rectangular cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/147—Lids or covers
  • H01M50/155—Lids or covers characterised by the material
  • H01M50/16—Organic 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
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/172—Arrangements of electric connectors penetrating the casing
  • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
  • H01M50/176—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for prismatic or rectangular cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/172—Arrangements of electric connectors penetrating the casing
  • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
  • H01M50/178—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for pouch or flexible bag cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/531—Electrode connections inside a battery casing
  • H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/543—Terminals
  • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/543—Terminals
  • H01M50/562—Terminals characterised by the material
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to an electricity storage device, an electrode terminal unit, and an exterior body set.
• Patent Document 1 discloses a storage cell.
• the storage cell includes a battery element and an exterior body that houses the battery element.
• the exterior body has a cylindrical sheet member and a first resin member that is joined to the sheet member so as to close a first opening of the sheet member.
• the storage cell further includes a positive electrode tab and a negative electrode tab that are electrically connected to the battery element.
• the positive electrode tab and the negative electrode tab are led out to the exterior body through a sealing portion between the inner surface of the sheet member and the first resin member.
• the sealing portion is made of the same resin member as the first resin member.
• thermal shock test heat shock test
• the test item is exposed to an environment in which rapid temperature changes are repeated, and the resistance of the test item to temperature changes is evaluated.
• deformation may occur in the tabs fixed to the resin member, i.e., the electrode terminals.
• this fact is not taken into consideration in Patent Document 1.
• the present invention aims to provide an electricity storage device in which the electrode terminals have improved resistance to deformation due to temperature changes.
• the power storage device includes an electrode body, an exterior body, and an electrode terminal.
• the exterior body seals the electrode body.
• the electrode terminal has one end and the other end arranged along a first direction, the one end is connected to the electrode body, and the other end is an electrode terminal that protrudes to the outside of the exterior body, and is made of a first material.
• the exterior body has a fixing member between the one end and the other end of the electrode terminal, which is fixed to the electrode terminal along a second direction intersecting with the first direction, and is made of a second material different from the first material.
• HV Vickers hardness of the first material
• T (mm) the thickness of the electrode terminal along a direction perpendicular to the first direction and the second direction
• ⁇ 1 the linear expansion coefficient of the first material
• ⁇ 2 the linear expansion coefficient of the second material
• L0 (mm) the length by which the electrode terminal is fixed to the fixing member along the second direction.
• the energy storage device is the energy storage device according to the first aspect, in which the first material is a metal and the second material is a resin.
• An electrode terminal unit for an electricity storage device includes an electrode terminal and a fixing member.
• the electrode terminal has one end and the other end arranged along a first direction, the one end is configured to be connected to an electrode body of the electricity storage device, and is made of a first material.
• the fixing member is fixed to the electrode terminal between the one end and the other end of the electrode terminal along a second direction intersecting with the first direction, and is made of a second material different from the first material.
• HV Vickers hardness of the first material
• T (mm) the thickness of the electrode terminal along a direction perpendicular to the first direction and the second direction
• ⁇ 1 the linear expansion coefficient of the first material
• ⁇ 2 the linear expansion coefficient of the second material
• L0 (mm) the length by which the electrode terminal is fixed to the fixing member along the second direction.
• the exterior body set for an electricity storage device comprises an electrode terminal unit for an electricity storage device according to the third aspect, and an exterior film joined to the electrode terminal unit.
• the present invention provides an electricity storage device in which the electrode terminals have improved resistance to deformation due to temperature changes.
• FIG. 1 is a perspective view illustrating a schematic diagram of an electricity storage device according to an embodiment.
• FIG. 2 is a cross-sectional view showing an example of a layer structure of the exterior member of FIG. 1 .
• FIG. 4 is a perspective view showing a schematic configuration of a fixing member.
• FIG. 2 is a perspective view showing a schematic configuration of an electrode terminal and its surroundings according to an embodiment;
• FIG. 11 is a perspective view showing a schematic configuration of an electrode terminal and its surroundings according to another embodiment.
• FIG. 2 is a cross-sectional view showing an example of a fixing member and a barrier film bonded thereto.
• FIG. 2 is a cross-sectional view showing an example of a layer structure of a barrier film.
• FIG. 2 is a cross-sectional view showing another example of the layer structure of a barrier film.
• FIG. 2 is a cross-sectional view showing still another example of the layer structure of the barrier film.
• a numerical range indicated by “to” means “greater than or equal to” or “less than or equal to”.
• the notation 2 to 15 mm means 2 mm or more and 15 mm or less.
• the upper limit or lower limit value described in a certain numerical range may be replaced with the upper limit or lower limit value of another numerical range described in stages.
• separately described upper and lower limits, upper and lower limits, or lower and lower limits may each be combined to form a numerical range.
• Fig. 1 is a perspective view that shows a schematic diagram of an electricity storage device 10 according to the present embodiment.
• the direction of the arrow UD indicates the thickness direction of the electricity storage device 10
• the direction of the arrow LR indicates the width direction of the electricity storage device 10.
• the direction of the arrow FB indicates the depth direction of the electricity storage device 10.
• the directions shown by the arrows UDLRFB are the same in the subsequent figures.
• the power storage device 10 includes an electrode body 20, an electrode terminal 30, and an exterior body 40.
• the electrode body 20 includes electrodes (positive and negative electrodes) constituting a power storage member such as a lithium ion battery, a capacitor, an all-solid-state battery, a semi-solid battery, a quasi-solid battery, a polymer battery, an all-resin battery, a lead-acid battery, a nickel-metal hydride battery, a nickel-cadmium battery, a nickel-iron battery, a nickel-zinc battery, a silver oxide-zinc battery, a metal-air battery, a polyvalent cation battery, or a capacitor, as well as a separator.
• a power storage member such as a lithium ion battery, a capacitor, an all-solid-state battery, a semi-solid battery, a quasi-solid battery, a polymer battery, an all-resin battery, a lead-acid battery, a nickel-metal hydride battery, a nickel-
• the shape of the electrode body 20 is an approximately rectangular parallelepiped.
• approximately rectangular parallelepiped includes, in addition to a perfect rectangular parallelepiped, a solid body that can be regarded as a rectangular parallelepiped by modifying the shape of a portion of the outer surface, for example.
• the shape of the electrode body 20 may be, for example, a cylinder or a polygonal prism.
• the exterior body 40 seals the electrode body 20.
• the exterior body 40 includes an exterior film 50 and a pair of lid bodies 60.
• the exterior film 50 wraps the electrode body 20 so that a pair of openings 40A are formed.
• the exterior film 50 is wrapped around the electrode body 20 so that a pair of openings 40A are formed.
• wrapping the electrode body 20 with the exterior film 50 is not limited to wrapping the exterior film 50, and the electrode body 20 may be placed inside the exterior film 50 that has been formed in a cylindrical shape in advance.
• the exterior film 50 has a protruding portion 50X that protrudes outward from the portion wrapping the electrode body 20 when the exterior film 50 wraps the electrode body 20.
• the pair of lid bodies 60 are respectively arranged on the sides of the electrode body 20 so as to close the pair of openings 40A. As described later, the pair of lid bodies 60 is an example of a fixing member of the present invention.
• [Exterior film] 2 is a cross-sectional view showing a layer structure of the exterior film 50 included in the power storage device 10 of FIG. 1.
• the exterior film 50 is, for example, a laminate (laminate film) having a base layer 51, a barrier layer 52, and a heat-sealable resin layer 53 in this order.
• the exterior film 50 does not need to include all of these layers, and may not include the barrier layer 52, for example. That is, the exterior film 50 may be made of a material that is flexible and easy to bend, and may be made of, for example, a resin film.
• the exterior film 50 may have the heat-sealable resin layer 53 as the innermost layer and the outermost layer. In this case, the exterior film 50 may wrap the electrode body 20 and the lid body 60 by bonding the outermost layer and the innermost layer.
• the substrate layer 51 is a layer for imparting heat resistance to the exterior film 50 and suppressing the occurrence of pinholes that may occur during processing or distribution.
• the substrate layer 51 is composed of, for example, at least one layer of a stretched polyester resin layer and a stretched polyamide resin layer.
• the substrate layer 51 includes at least one layer of a stretched polyester resin layer and a stretched polyamide resin layer, so that the barrier layer 52 can be protected during processing of the exterior film 50 and breakage of the exterior film 50 can be suppressed.
• the stretched polyester resin layer is preferably a biaxially stretched polyester resin layer
• the stretched polyamide resin layer is preferably a biaxially stretched polyamide resin layer.
• the stretched polyester resin layer is more preferably a biaxially stretched polyethylene terephthalate (PET) film
• the stretched polyamide resin layer is more preferably a biaxially stretched nylon (ONy) film.
• the substrate layer 51 may be composed of both a stretched polyester resin layer and a stretched polyamide resin layer. From the standpoint of film strength, the thickness of the base layer 51 is preferably, for example, 5 to 300 ⁇ m, and more preferably 5 to 150 ⁇ m.
• the barrier layer 52 is bonded to the base layer 51, for example, via an adhesive layer 54.
• the barrier layer 52 included in the exterior film 50 is composed of, for example, a metal foil having barrier properties, from the viewpoint of workability such as moisture resistance and extensibility, and cost.
• the metal foil include aluminum alloy, stainless steel, titanium steel, and steel plate.
• the aluminum alloy foil preferably contains iron from the viewpoint of packaging suitability and pinhole resistance when packaging the electrode body 20.
• the iron content in the aluminum alloy foil is preferably 0.5 to 5.0 mass%, and more preferably 0.7 to 2.0 mass%.
• the exterior film 50 can obtain packaging suitability, excellent pinhole resistance, and extensibility.
• the exterior film 50 can obtain excellent flexibility.
• the barrier layer 52 may contain a vapor deposition film and a resin layer.
• the thickness of the barrier layer 52 is preferably, for example, 5 to 200 ⁇ m, and more preferably 30 to 80 ⁇ m, in terms of barrier properties, pinhole resistance, and packaging suitability.
• the thickness of the barrier layer 52 is 15 ⁇ m or more, the exterior film 50 is less likely to break even when stress is applied during packaging processing.
• the thickness of the barrier layer 52 is 200 ⁇ m or less, the increase in mass of the exterior film 50 can be reduced, and a decrease in the weight energy density of the electricity storage device 10 can be suppressed.
• the barrier layer 52 when the barrier layer 52 is an aluminum foil, it is preferable that at least the surface opposite to the base layer 51 is provided with a corrosion-resistant film in order to prevent dissolution and corrosion.
• the barrier layer 52 may be provided with a corrosion-resistant film on both sides.
• the corrosion-resistant film refers to a thin film that is provided with corrosion resistance (e.g., acid resistance, alkali resistance, etc.) on the barrier layer 52 by performing, for example, hydrothermal conversion treatment such as boehmite treatment, chemical conversion treatment, anodizing treatment, plating treatment such as nickel or chromium, or corrosion prevention treatment by applying a coating agent on the surface of the barrier layer 52.
• the corrosion-resistant film means a film that improves the acid resistance of the barrier layer 52 (acid-resistant film), a film that improves the alkali resistance of the barrier layer 52 (alkali-resistant film), etc.
• the treatment for forming the corrosion-resistant film may be one type, or two or more types may be combined. In addition, it can be formed into not only one layer but also multiple layers.
• hydrothermal conversion treatment and anodizing treatment are treatments in which the metal foil surface is dissolved by a treatment agent to form metal compounds with excellent corrosion resistance. Note that these treatments may also be included in the definition of chemical conversion treatment.
• the barrier layer 52 has a corrosion-resistant coating
• the corrosion-resistant coating is also included in the barrier layer 52.
• the corrosion-resistant coating prevents delamination between the barrier layer 52 (e.g., aluminum alloy foil) and the base layer 51 during molding of the exterior film 50, prevents dissolution and corrosion of the surface of the barrier layer 52 due to hydrogen fluoride produced by the reaction between the electrolyte and moisture, and in particular prevents dissolution and corrosion of aluminum oxide present on the surface of the barrier layer 52 when the barrier layer 52 is an aluminum alloy foil, and improves the adhesion (wettability) of the surface of the barrier layer 52, preventing delamination between the base layer 51 and the barrier layer 52 during heat sealing and between the base layer 51 and the barrier layer 52 during molding.
• the barrier layer 52 e.g., aluminum alloy foil
• the heat-sealable resin layer 53 is bonded to the barrier layer 52, for example, via an adhesive layer 55.
• the heat-sealable resin layer 53 included in the exterior film 50 is a layer that provides the exterior film 50 with heat-sealing sealability.
• Examples of the heat-sealable resin layer 53 include resin films made of polyester resins such as polyethylene terephthalate resins and polybutylene terephthalate resins, polyolefin resins such as polyethylene resins and polypropylene resins, or acid-modified polyolefin resins obtained by graft-modifying these polyolefin resins with an acid such as maleic anhydride. From the standpoint of sealability and strength, the thickness of the heat-sealable resin layer 53 is preferably, for example, 20 to 300 ⁇ m, and more preferably 40 to 150 ⁇ m.
• the exterior film 50 has one or more layers with a buffer function (hereinafter referred to as "buffer layers") outside the heat-sealable resin layer 53, and more preferably outside the barrier layer 52.
• the buffer layer may be laminated on the outside of the base layer 51, or the base layer 51 may also function as a buffer layer.
• the multiple buffer layers may be adjacent to each other, or may be laminated via the base layer 51, the barrier layer 52, etc.
• the material constituting the buffer layer can be selected from any material having cushioning properties.
• the material having cushioning properties is, for example, rubber, nonwoven fabric, or foam sheet.
• the rubber is, for example, natural rubber, fluororubber, or silicone rubber.
• the rubber hardness is preferably about 20 to 90.
• the material constituting the nonwoven fabric is preferably a material having excellent heat resistance.
• the lower limit of the thickness of the buffer layer is preferably 100 ⁇ m, more preferably 200 ⁇ m, and even more preferably 1000 ⁇ m.
• the upper limit of the thickness of the buffer layer is preferably 5000 ⁇ m, and even more preferably 3000 ⁇ m.
• the preferred range of thickness of the buffer layer is 100 ⁇ m to 5000 ⁇ m, 100 ⁇ m to 3000 ⁇ m, 200 ⁇ m to 5000 ⁇ m, 200 ⁇ m to 3000 ⁇ m, 1000 ⁇ m to 5000 ⁇ m, or 1000 ⁇ m to 3000 ⁇ m.
• the most preferred range of thickness of the buffer layer is 1000 ⁇ m to 3000 ⁇ m.
• the lower limit of the thickness of the buffer layer is preferably 0.5 mm.
• the upper limit of the thickness of the buffer layer is preferably 10 mm, more preferably 5 mm, and even more preferably 2 mm.
• the preferred range of the thickness of the buffer layer is 0.5 mm to 10 mm, 0.5 mm to 5 mm, or 0.5 mm to 2 mm.
• the buffer layer functions as a cushion, preventing the exterior film 50 from being damaged by impact when the energy storage device 10 is dropped or by handling during the manufacture of the energy storage device 10.
• a storage portion in the exterior film 50 through cold forming to accommodate the electrode body 20.
• the exterior body 40 seals the electrode body 20 by wrapping the exterior film 50 around the electrode body 20, so that the electrode body 20 can be easily sealed regardless of the thickness of the electrode body 20.
• the exterior film 50 is wrapped so as to contact the outer surface of the electrode body 20.
• the exterior film 50 is wrapped around the outer surface of the electrode body 20 so that it is in contact with the outer surface of the electrode body 20.
• the exterior film 50 is wrapped around the electrode body 20 to have an opening 40A, and the surfaces (thermally adhesive resin layer 53) of the exterior film 50 that face each other in the protruding portion 50X are heat sealed to form the first sealing portion 70.
• the protruding portion 50X includes a portion where a pair of opposing edges of the exterior film 50 shown in FIG. 2 are overlapped.
• the first sealing portion 70 extends in the longitudinal direction (FB direction) of the exterior body 40.
• the position where the first sealing portion 70 is formed in the exterior body 40 can be selected arbitrarily.
• the root 70X of the first sealing portion 70 is preferably located on the edge 43 at the boundary between the first surface 41 and the second surface 42 of the exterior body 40.
• the first surface 41 has a larger area than the second surface 42.
• the root 70X of the first sealing portion 70 may be located on any surface of the exterior body 40.
• the protruding portion 50X is folded, for example, to the first surface 41 or the second surface 42 of the exterior body 40. In this embodiment, when the power storage device 10 is in use, the protruding portion 50X is folded toward the second surface 42 of the exterior body 40.
• the second sealing portion 80 is formed by heat sealing the heat-sealable resin layer 53 of the exterior film 50 to the lid seal portion 63 of the lid body 60 described below.
• the exterior film 50 is joined to the lid body 60.
• [Fixing member] 3 is a perspective view of the lid body 60 according to the present embodiment.
• the lid body 60 is, for example, a substantially rectangular plate, and constitutes the exterior body 40 together with the exterior film 50.
• the lid body 60 is made of a second material.
• "made of a second material” means that the content of the second material is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, when the entire material constituting the lid body 60 is taken as 100% by mass. That is, the material constituting the lid body 60 can contain, in addition to the second material, a material other than the second material.
• the second material in this embodiment is a resin.
• resins include resins such as polyester, polyolefin, polyamide, epoxy resin, acrylic resin, fluororesin, polyurethane, silicone resin, and phenol resin, as well as thermoplastic resins such as modified versions of these resins.
• the second material may be a mixture of these resins, a copolymer, or a modified version of a copolymer.
• the second material is preferably a heat-sealable resin such as polyester or polyolefin, and more preferably polyolefin.
• the lid 60 may be molded by any molding method.
• polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolymer polyesters.
• copolymer polyesters include copolymer polyesters in which ethylene terephthalate is the main repeating unit.
• copolymer polyesters in which ethylene terephthalate is the main repeating unit and is polymerized with ethylene isophthalate (hereinafter abbreviated as polyethylene (terephthalate/isophthalate)), polyethylene (terephthalate/adipate), polyethylene (terephthalate/sodium sulfoisophthalate), polyethylene (terephthalate/sodium isophthalate), polyethylene (terephthalate/phenyl-dicarboxylate), and polyethylene (terephthalate/decanedicarboxylate).
• the second material is polybutylene terephthalate from the viewpoint of increasing heat resistance and pressure resistance.
• polyolefins include polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene; ethylene- ⁇ -olefin copolymers; polypropylenes such as homopolypropylene, block copolymers of polypropylene (e.g., block copolymers of propylene and ethylene), and random copolymers of polypropylene (e.g., random copolymers of propylene and ethylene); propylene- ⁇ -olefin copolymers; and ethylene-butene-propylene terpolymers.
• polyolefin resin is a copolymer, it may be a block copolymer or a random copolymer. Of these, polypropylene is preferred as the second material because of its excellent thermal adhesion and electrolyte resistance.
• the resin as the second material may contain a filler as necessary.
• fillers include glass beads, graphite, glass fiber, and carbon fiber.
• the lid body 60 has a first surface 61, a second surface 62, and a lid seal portion 63.
• the first surface 61 faces the electrode body 20.
• the second surface 62 is the surface opposite to the first surface 61.
• the lid seal portion 63 is connected to the first surface 61 and the second surface 62, and is heat-sealed to the heat-sealable resin layer 53 of the exterior film 50.
• the lid seal portion 63 includes a first seal surface 63A, a second seal surface 63B, a third seal surface 63C, and a fourth seal surface 63D.
• the first seal surface 63A constitutes the upper surface of the lid body 60.
• the first seal surface 63A extends in the width direction (LR direction) of the energy storage device 10 when the lid body 60 is viewed from the front.
• the second seal surface 63B and the third seal surface 63C are connected to the first seal surface 63A and constitute the side surfaces of the lid body 60.
• the second sealing surface 63B and the third sealing surface 63C extend in a thickness direction (UD direction) of the electricity storage device 10 that intersects with the width direction when the lid body 60 is viewed from the front.
• UD direction thickness direction
• the width direction and the thickness direction of the electricity storage device 10 are perpendicular to each other.
• the fourth sealing surface 63D forms the lower surface of the lid body 60.
• the fourth sealing surface 63D extends in the width direction (LR direction) when the lid body 60 is viewed from the front.
• a through hole 60X is formed penetrating the first surface 61 and the second surface 62.
• the through hole 60X is rectangular in a front view of the lid body 60.
• the electrode terminal 30 penetrates the through hole 60X so as to protrude to the outside of the exterior body 40.
• the inner wall surface of the through hole 60X and the outer circumferential surface of the electrode terminal 30 facing the inner wall surface are adhesively fixed to each other via an adhesive film 31, which will be described later.
• the lid body 60 is fixed to the electrode terminal 30 along the second direction between one end 300 and the other end 301 of the electrode terminal 30.
• the lid body 60 to which the electrode terminal 30 is fixed as shown in FIG. 4, may be referred to as an electrode terminal unit 600.
• the lid body 60 When the lid body 60 is plate-shaped, it is preferable that the lid body 60 has a certain degree of thickness so that deformation of the exterior body 40 is suppressed even when the power storage device 10 is arranged on top of each other. From another perspective, when the lid body 60 is plate-shaped, it is preferable that the lid seal portion 63 of the lid body 60 has a certain degree of thickness so that the lid seal portion 63 of the lid body 60 and the exterior film 50 can be suitably heat-sealed when forming the second sealing portion 80.
• the minimum value of the thickness of the lid body 60 is, for example, 1.0 mm, more preferably 3.0 mm, and even more preferably 4.0 mm.
• the maximum value of the thickness of the lid body 60 is, for example, 20 mm, more preferably 15 mm, and even more preferably 12 mm.
• the preferred ranges of thickness of the material constituting the lid body 60 are 1.0 mm to 20 mm, 1.0 mm to 15 mm, 1.0 mm to 12 mm, 3.0 mm to 20 mm, 3.0 mm to 15 mm, 3.0 mm to 12 mm, 4.0 mm to 20 mm, 4.0 mm to 15 mm, and 4.0 mm to 12 mm.
• the material constituting the lid body 60 does not include films defined by the JIS (Japanese Industrial Standards) [Packaging Terminology] standard.
• the thickness of the lid body 60 may vary depending on the part of the lid body 60. When the thickness of the lid body 60 varies depending on the part, the thickness of the lid body 60 is the thickness of the thickest part.
• a barrier film 90 may be bonded to the lid body 60 from the viewpoint of suppressing the intrusion of at least one of moisture and gas into the interior of the exterior body 40 from between the lid body 60 and the exterior film 50.
• the barrier film 90 may cover at least a portion of the lid seal portion 63 of the lid body 60.
• the barrier film 90 covers the entire lid seal portion 63, the second surface 62, and the inside of the through hole 60X of the lid body 60.
• the barrier film 90 may cover the boundaries 64 to 67.
• the barrier film 90 covers the lid seal portion 63 and the boundaries 64 to 67, as well as the second surface 62 and the inside of the through hole 60X, the intrusion of moisture into the interior of the exterior body 40 from between the electrode terminal 30 and the through hole 60X is suppressed.
• the barrier film 90 may be composed of a single film, or, for example, the portion covering the lid seal portion 63 and the portion covering the second surface 62 may be composed separately. In other words, the barrier film 90 may be composed of multiple divided films.
• FIG. 6 is a cross-sectional view showing an example of a lid body 60 and a barrier film 90 bonded thereto.
• the position of the end 90A of the portion of the barrier film 90 covering the lid seal portion 63 and the position of the end 90B of the portion covering the inside of the through-hole 60X of the lid body 60 can be selected arbitrarily. If the energy storage device 10 is a battery containing an electrolyte solution, such as a lithium ion battery, the ends 90A and 90B of the barrier film 90 may come into contact with gas such as hydrogen fluoride generated from the electrolyte solution, which may corrode the barrier layer 91 provided on the barrier film 90, which will be described later.
• gas such as hydrogen fluoride generated from the electrolyte solution
• the end 90A is located closer to the second surface 62 than the boundary between the lid seal portion 63 and the first surface 61.
• the end 90B is located closer to the opening of the through hole 60X on the second surface 62 side than the opening on the first surface 61 side.
• the end 90A may be located at the boundary between the lid seal portion 63 and the first surface 61, or may extend to a position closer to the electrode body 20 than the lid body 60.
• the end 90B may be located near the opening of the through hole 60X on the first surface 61 side, or may extend to a position closer to the electrode body 20 than the lid body 60.
• the barrier film 90 may include at least a barrier layer 91.
• the specifications of the barrier layer 91 are the same as the specifications of the barrier layer 52 of the exterior film 50.
• the barrier layer 91 may be thinner than the barrier layer 52 of the exterior film 50.
• the barrier film 90 may include an outer layer 92 laminated on the surface of the barrier layer 91 opposite to the surface to be joined to the lid body 60.
• the outer layer 92 for example, serves as a base layer or a heat-sealable resin layer.
• the role of the base layer is to protect the barrier layer 91.
• the role of the heat-sealable resin layer is to be heat-sealed with the heat-sealable resin layer 53 of the exterior film 50.
• the outer layer 92 serves as a base layer
• the specifications of the outer layer 92 as a base layer are the same as the specifications of the base layer 51 of the exterior film 50.
• the specifications of the outer layer 92 as a heat-sealable resin layer are the same as the specifications of the heat-sealable resin layer 53 of the exterior film 50.
• the specifications of the outer layer 92 as a heat-sealable resin layer are the same as the specifications of the heat-sealable resin layer 53 of the exterior film 50.
• the outer layer 92 may be thinner than the heat-sealable resin layer 53.
• the thickness of the outer layer 92 may be, for example, 5 to 20 ⁇ m.
• the barrier layer 91 is protected.
• the outer layer 92 is a base layer, the outer layer 92 and the heat-sealable resin layer 53 are bonded, for example, with an adhesive or the like.
• the outer layer 92 is a heat-sealable resin layer, the outer layer 92 and the heat-sealable resin layer 53 can be suitably bonded by heat fusion.
• the barrier layer 91 and the outer layer 92 may be bonded with an adhesive layer 54.
• the barrier film 90 may include a heat-sealable resin layer 93 laminated on the surface of the barrier layer 91 that is to be joined to the lid 60.
• the specifications of the heat-sealable resin layer 93 are the same as those of the heat-sealable resin layer 53 of the exterior film 50.
• the heat-sealable resin layer 93 may be thinner than the heat-sealable resin layer 53.
• the thickness of the heat-sealable resin layer 93 may be, for example, 5 to 20 ⁇ m.
• the material constituting the lid 60 does not include the material constituting the barrier film 90.
• Electrode terminal 4 is a perspective view showing a configuration near the electrode terminal 30.
• the electrode terminal 30 is a conductive member electrically connected to the electrode body 20 (positive electrode or negative electrode) and is a terminal used for inputting and outputting power in the electrode body 20.
• the electrode terminal 30 according to this embodiment is formed, for example, in a plate shape having a thickness.
• the thickness of the electrode terminal 30 is defined as T (mm).
• the thickness T is the average value of thickness values measured at three points arbitrarily extracted from the portion of the electrode terminal 30 that is fixed to the lid body 60.
• the thickness direction of the electrode terminal 30 coincides with the thickness direction (UD direction) of the electricity storage device 10.
• the electrode terminal 30 has one end 300 and the other end 301 arranged along a first direction.
• the first direction coincides with the depth direction (FB direction) of the energy storage device 10.
• the one end 300 of the electrode terminal 30 is connected to the electrode body 20.
• the other end 301 of the electrode terminal 30 protrudes outside the exterior body 40.
• the electrode terminal 30 is made of a first material.
• “made of a first material” means that, when the entire material constituting the electrode terminal 30 is taken as 100% by mass, the content of the first material is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
• the electrode terminal 30 is made of a metal containing an alloy
• the metal is the first material.
• the electrode terminal 30 is made of a main body made of a metal containing an alloy and a metal containing an alloy and has a plating layer laminated on the outer surface of the main body, the metal constituting the main body is the first material.
• the first material in this embodiment is a metal.
• the metal is, for example, aluminum, nickel, copper, or an alloy thereof.
• the first material of the electrode terminal 30 connected to the positive electrode is usually aluminum or an aluminum alloy.
• the first material of the electrode terminal 30 connected to the negative electrode is usually copper, nickel, or a copper alloy.
• the electrode terminal 30 can be a body made of copper, which is the first material, and nickel-plated.
• the surface of the electrode terminal 30 is preferably subjected to a chemical conversion treatment in order to enhance resistance to electrolyte.
• a chemical conversion treatment include known methods for forming a corrosion-resistant film using phosphates, chromates, fluorides, triazine thiol compounds, etc.
• a preferred method is a phosphate chromate treatment using a compound consisting of three components: phenolic resin, chromium (III) fluoride compound, and phosphoric acid.
• the adhesive film 31 is bonded to the outer peripheral surface of the electrode terminal 30 according to this embodiment.
• the adhesive film 31 can be any film that can bond the electrode terminal 30 made of a metal as the first material and the lid body 60 made of a resin as the second material.
• the adhesive film 31 can be, for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin, a cyclic polyolefin resin, or an acid-modified polyolefin resin obtained by graft-modifying these polyolefin resins with an acid such as maleic anhydride.
• the adhesive film 31 can be a single layer or two or more layers of these films. In this embodiment, the adhesive film 31 is bonded to at least the entire portion of the outer peripheral surface of the electrode terminal 30 that faces the inner wall surface of the through hole 60X.
• the length L0 is equal to (L1 x 2), where L1 is the length of the electrode terminal 30 along the second direction.
• the length L1 is the average of the lengths measured in the second direction at three locations arbitrarily selected from the portion of the electrode terminal 30 that is fixed to the lid 60.
• the thermal shock test is a test for evaluating the deformation resistance of the electricity storage device 10 against temperature changes.
• the thermal shock test can be performed, for example, by using a test device that repeatedly moves a sample cage housing the electricity storage device 10 between a low temperature chamber and a high temperature chamber, thereby subjecting the electricity storage device 10 to a rapid temperature change.
• the temperature of the low temperature chamber is maintained at, for example, ⁇ 40° C., ⁇ 30° C., or ⁇ 20° C.
• the temperature of the high temperature chamber is maintained at, for example, 60° C., 70° C., or 80° C.
• the number of cycles of movement of the sample cage housing the electricity storage device 10 is, for example, 100 to 1500 times.
• the degree of deformation of the electrode terminal 30 in a thermal shock test is contributed by the Vickers hardness h (HV) of the first material, the thickness T (mm), the length L0 (mm), the linear expansion coefficient ⁇ 1 (10 -6 /°C) of the first material, and the linear expansion coefficient ⁇ 2 (10 -6 /°C) of the second material.
• HV Vickers hardness
• ⁇ 1 10 -6 /°C
• ⁇ 2 10 -6 /°C
• the "deformation yield strength P (mm x HV2 )," which is an index showing the deformation resistance of the electrode terminal 30 in a thermal shock test is defined as the following formula (1).
• P (h ⁇ T) 2 ⁇ ( ⁇ 1/ ⁇ 2) ⁇ L0
• the structure and properties of the electrode terminal 30 itself contribute to the ease of deformation of the electrode terminal 30, and it is considered that the greater the thickness T or the greater the Vickers hardness h of the first material, the more the deformation is suppressed.
• the fixing mechanism between the electrode terminal 30 and the lid body 60 and the difference in the relative physical properties of the two also contribute to the ease of deformation of the electrode terminal 30. Specifically, it is considered that the shorter the length of the electrode terminal 30 fixed to the inner wall surface of the through hole 60X along the second direction, the less the electrode terminal 30 is affected by dimensional changes due to temperature changes in the lid body 60, and the more the deformation is suppressed.
• the difference in the rate of dimensional change due to temperature change between the electrode terminal 30 and the lid 60 can be specifically expressed as the ratio of the linear expansion coefficient ⁇ 1 of the first material to the linear expansion coefficient ⁇ 2 of the second material ( ⁇ 1/ ⁇ 2).
• the inventors have confirmed through experiments that if the deformation resistance P calculated according to the above formula is less than 0.222, visible deformation occurs in the electrode terminal 30 when 100 cycles of temperature changes from -40 to 70°C are performed.
• the deformation of the electrode terminal 30 is particularly noticeable in the portion from the periphery of the through hole 60X, which is the fixing portion between the electrode terminal 30 and the lid 60, to the other end 301.
• the inventors have confirmed that if the deformation resistance P is 0.222 or more, no visible deformation occurs in the electrode terminal 30 even when the same cycles are performed.
• the Vickers hardness h is evaluated by pressing a square pyramidal diamond indenter into the test surface of one sample of the first material under a predetermined test force F (N) at a test temperature of 23°C, and calculating the average length d (mm) of a pair of diagonals of the indentation left on the sample surface after the test load is released.
• the test surface of the sample is assumed to coincide with the surface facing the UD direction in the electrode terminal 30.
• the test force F when measuring the Vickers hardness h is 1.961 N
• the pressing speed of the diamond indenter is 0.1 mm/s
• the time to reach the test force F is 4 seconds
• the test force is held for 12 seconds.
• Other measurement conditions are as described in JIS Z2244-1:2020.
• a sample of the first material can be obtained by removing the plating from the electrode terminal.
• the linear expansion coefficient for metals is a value measured by a push-in test using a dilatometric thermomechanical analyzer as specified in JIS Z 2285:2003, with one sample of the metal being subjected to the dilatometric thermomechanical analyzer as specified in JIS Z 2285:2003.
• the metal sample is a cube of 1 mm length x 1 mm width x 1 mm thickness, with the length direction coinciding with the FB direction of the electrode terminal 30, the width direction coinciding with the LR direction of the electrode terminal 30, and the thickness direction coinciding with the UD direction of the electrode terminal 30.
• the longitudinal ends of the metal sample shall have a parallelism tolerance of 25 ⁇ m as specified in JIS B 0621.
• the push-in load using the dilatometric thermomechanical analyzer shall be 10 g, the measurement temperature range shall be 20°C to 300°C, and the temperature rise rate shall be 5°C/min.
• the standard material shall be quartz glass with the same shape and dimensions as the sample and the recommended values for thermal expansion and linear expansion coefficient.
• the linear expansion coefficient of the resin is measured by subjecting one test piece of the resin to a thermomechanical analysis (TMA) device specified in JIS K 7197:2012 and carrying out an indentation test, in accordance with the method specified in JIS K 7197:2012.
• TMA thermomechanical analysis
• the test piece of the resin is a cube of length 1 mm x width 1 mm x thickness 1 mm, with the length direction coinciding with the FB direction of the lid 60, the width direction coinciding with the LR direction of the lid 60, and the thickness direction coinciding with the UD direction of the lid 60.
• the parallelism of both ends of the test piece of the resin in the length direction is ⁇ 25 ⁇ m.
• the indentation load by the thermomechanical analysis device is 10 g, the measurement temperature range is 20°C to 120°C, and the temperature rise rate is 5°C/min.
• the method for measuring the linear expansion coefficient of the first material may be changed.
• the metal sample obtained from the electrode terminal may have a size of 15 mm length (FB direction at the electrode terminal) x 3 mm width (LR direction at the electrode terminal) x obtainable thickness (UD direction at the electrode terminal).
• the linear expansion coefficient of the first material is the ratio of the change in length of the sample to the temperature measured by pulling the metal sample in the length direction using the thermomechanical analyzer.
• the measurement temperature range in this measurement is 20°C to 300°C, and the temperature rise rate is 5°C/min.
• the tensile load in the tensile test using the thermomechanical analyzer is 4 g.
• the method for measuring the linear expansion coefficient of the second material may be changed.
• the resin test piece obtained from the lid can have a size of 15 mm length (FB direction in the lid) x 3 mm width (LR direction in the lid) x extractable thickness (UD direction in the lid).
• the linear expansion coefficient of the second material is the ratio of the change in length of the test piece to the temperature, measured by pulling the resin test piece in the length direction using the thermomechanical analyzer.
• the measurement temperature range in this measurement is 20°C to 120°C, and the temperature rise rate is 5°C/min.
• the tensile load in the tensile test using the thermomechanical analyzer is 4 g.
• the electrode terminal 30 is fixed to the lid body 60 so as to pass through the through hole 60X of the lid body 60.
• the deformation resistance P can be calculated by applying the above formula (1).
• the length L0 (mm) of the electrode terminal 30 fixed to the lid body 60 along the second direction is equal to the length L1 (mm) of the electrode terminal 30 along the second direction.
• the electrode terminal 30 fixed to the lid body 60 as shown in FIG. 5 may be referred to as an electrode terminal unit 601.
• the exterior body 40 had an exterior film 50 and a pair of lid bodies 60.
• the configuration of the exterior body 40 is not limited to that of the above embodiment.
• the exterior film 50 does not have to be wrapped around the outer surface of the electrode body 20 so as to be in contact with it.
• the location where the protrusion 50X is formed is not limited to that of the above embodiment, and the protrusion 50X itself may be omitted.
• the electrode body may be sealed using multiple plate-shaped members made of the same material as the material constituting the lid body 60.
• the second material is not limited to the resin exemplified in the above embodiment.
• the second material may be, for example, a metal oxide, a carbon fiber reinforced plastic, or a rubber material, or may be a combination of two or more of these materials, or a combination of at least one of these materials and a resin.
• the electrode body 20 may be fixed to the lid body 60 without using the adhesive film 31.
• the electrode body 20 and the lid body 60 may be fixed, for example, by a heat-sealing resin that fills the gap between them, or by an adhesive.
• the exterior film 50 of the power storage device 10 may extend outward beyond the lid body 60 in the depth direction (FB direction).
• the portion of the exterior film 50 that extends beyond the lid body 60 may be folded like a Gabeltop pouch or a brick pouch.
• the lid body 60 is not limited to being approximately rectangular. For example, it may be approximately circular, approximately elliptical, or approximately polygonal.
• the present invention further includes the following embodiments.
• the present invention can be embodied not only as an electricity storage device 10, but also as an electrode terminal unit 600, 601 for an electricity storage device that at least partially constitutes an exterior body 40 that seals an electrode body 20 of the electricity storage device 10.
• the electrode terminal units 600, 601 include an electrode terminal 30 and a fixing member (a cover body 60).
• the electrode terminal 30 has one end 300 and the other end 301 that are arranged along a first direction, and is configured so that the one end 300 is connected to the electrode body 20 of the electricity storage device 10.
• the fixing member is fixed to the electrode terminal 30 between the one end 300 and the other end 301 of the electrode terminal 30 along a second direction that intersects with the first direction, and is made of a second material different from the first material.
• the Vickers hardness of the first material is h (HV)
• the thickness of the electrode terminal 30 along a direction perpendicular to the first direction and the second direction is T (mm)
• the linear expansion coefficient of the first material is ⁇ 1
• the linear expansion coefficient of the second material is ⁇ 2
• the length by which the electrode terminal is fixed to the fixing member along the second direction is L0 (mm)
• the electrode terminal units 600, 601 may each have an adhesive film 31 and a barrier film 90.
• the present invention can be implemented as an exterior body set for an electricity storage device that at least partially constitutes the exterior body 40 that seals the electrode body 20 of the electricity storage device 10.
• the exterior body set includes the electrode terminal unit 600 or 601 for the electricity storage device described in (1) and an exterior film 50 that is joined to the electrode terminal unit 600 or 601.
• a lid made of resin and an electrode terminal made of metal were prepared and fixed to each other using an adhesive resin to obtain samples of exterior bodies according to Examples 1 to 5 and Comparative Examples 1 and 2.
• the lid and the electrode terminal were formed to have a rectangular plate-like outer shape in each sample.
• the electrode terminal had one end and the other end along a first direction, and was fixed to the lid along a second direction perpendicular to the first direction between the one end and the other end. More specifically, the electrode terminal was fixed to the lid so that the first direction was parallel to the thickness direction of the lid and the second direction was parallel to the width direction of the lid.
• the fixing manner of the lid and the electrode terminal was two types: Mode 1 in which both sides of the electrode terminal were fixed so that the electrode terminal penetrated a through hole formed in the lid as shown in FIG. 4, and Mode 2 in which one side of the electrode terminal was fixed to the sealing surface of the lid as shown in FIG. 5.
• a common adhesive film was used to fix the lid and the electrode terminal in each sample.
• the Vickers hardness h, the linear expansion coefficient ⁇ 1, and the linear expansion coefficient ⁇ 2 were each measured by the method described above.
• Table 1 also shows the alloy symbols and quality symbols of the metals used as the materials constituting the electrode terminal.

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