WO2024053093A1 - 非水電解液電池用リード線及び非水電解液電池 - Google Patents

非水電解液電池用リード線及び非水電解液電池 Download PDF

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Publication number
WO2024053093A1
WO2024053093A1 PCT/JP2022/033901 JP2022033901W WO2024053093A1 WO 2024053093 A1 WO2024053093 A1 WO 2024053093A1 JP 2022033901 W JP2022033901 W JP 2022033901W WO 2024053093 A1 WO2024053093 A1 WO 2024053093A1
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Prior art keywords
conductor
electrolyte battery
aqueous electrolyte
lead wire
mass
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PCT/JP2022/033901
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English (en)
French (fr)
Japanese (ja)
Inventor
友多佳 松村
健吾 後藤
聡 安井
有佑 暮石
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Priority to PCT/JP2022/033901 priority Critical patent/WO2024053093A1/ja
Priority to CN202280099506.5A priority patent/CN119790542A/zh
Priority to KR1020257006798A priority patent/KR20250038806A/ko
Priority to JP2024545402A priority patent/JPWO2024053093A1/ja
Priority to US19/109,607 priority patent/US20260100487A1/en
Publication of WO2024053093A1 publication Critical patent/WO2024053093A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/571—Methods or arrangements for affording protection against corrosion; Selection of materials therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
    • H01M50/591—Covers
    • 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 disclosure relates to a lead wire for a non-aqueous electrolyte battery and a non-aqueous electrolyte battery.
  • a non-aqueous electrolyte battery in which a bag is used as an enclosure and a non-aqueous electrolyte, a positive electrode, and a negative electrode are sealed inside the bag.
  • a non-aqueous electrolyte an electrolyte in which a fluorine-containing lithium salt such as LiPF 6 or LiBF 4 is dissolved in propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, or the like is used.
  • the enclosure is required to have properties that prevent the permeation of electrolyte and gas and the infiltration of moisture from the outside. For this reason, a laminate film in which a metal layer such as aluminum foil is coated with a resin is used as a material for the enclosure, and the ends of the two laminate films are heat-sealed to form the enclosure.
  • One end of the enclosure is an opening, and a non-aqueous electrolyte, a positive electrode plate, a negative electrode plate, a separator, etc. are sealed inside. Furthermore, a lead conductor whose one end is connected to the positive electrode plate and the negative electrode plate is arranged so as to extend from the inside of the enclosure to the outside, and finally the opening is heat-sealed (thermal fusion) to open the enclosure. At the same time, the enclosure and the lead conductor are bonded together to seal the opening. The last part to be heat-sealed is called the seal part.
  • the portion of the lead conductor corresponding to the seal portion is coated with an insulating film, and a lead wire that includes an insulating film and a lead conductor is called a lead wire for non-aqueous electrolyte batteries (tab lead).
  • the enclosure and the lead conductor are bonded (thermal fused) via this insulating film. Therefore, this insulating film is required to have the property of being able to maintain adhesion between the lead conductor and the enclosure without causing a short circuit between the metal layer of the enclosure and the lead conductor.
  • a lead wire for a non-aqueous electrolyte battery includes a conductor and an insulating film having one or more layers and covering at least a portion of the outer peripheral surface of the conductor, wherein the conductor has at least a portion of the outer peripheral surface of the conductor.
  • the conductor coating contains a trivalent chromium compound containing chromium hydroxide and a metal element, and the conductor coating contains a trivalent chromium compound containing chromium on the outermost surface of the conductor coating, per unit area of chromium contained in the trivalent chromium compound on the outermost surface of the conductor coating.
  • the ratio of the mass [mg/m 2 ] of chromium per unit area contained in the chromium hydroxide to the mass [mg/m 2 ] of chromium hydroxide is 0.30 or more and 0.90 or less, and the insulating film is It has an innermost layer laminated on the surface, the innermost layer is mainly composed of a resin component containing maleic anhydride-modified polypropylene, and the acid modification rate of the resin component is 0.02% by mass or more and 0.50% by mass or less. be.
  • FIG. 1 is a perspective view of a lead wire for a non-aqueous electrolyte battery according to an embodiment of the present disclosure.
  • FIG. 2 is a partial cross-sectional view of a lead wire for a non-aqueous electrolyte battery according to an embodiment of the present disclosure.
  • FIG. 3 is a perspective view showing an example of a non-aqueous electrolyte battery including a lead wire for a non-aqueous electrolyte battery according to an embodiment of the present disclosure.
  • FIG. 4 is a longitudinal cross-sectional view of the non-aqueous electrolyte battery of FIG. 3.
  • tab leads are required to have improved resistance to non-aqueous electrolytes.
  • An object of the present disclosure is to provide a lead wire for a non-aqueous electrolyte battery that has excellent resistance to the non-aqueous electrolyte of the non-aqueous electrolyte battery.
  • a lead wire for a non-aqueous electrolyte battery includes a conductor and an insulating film having one or more layers and covering at least a portion of the outer peripheral surface of the conductor, wherein the conductor has at least a portion of the outer peripheral surface of the conductor.
  • the conductor coating contains a trivalent chromium compound containing chromium hydroxide and a metal element, and the conductor coating contains a trivalent chromium compound containing chromium on the outermost surface of the conductor coating, per unit area of chromium contained in the trivalent chromium compound on the outermost surface of the conductor coating.
  • the ratio of the mass [mg/m 2 ] of chromium per unit area contained in the chromium hydroxide to the mass [mg/m 2 ] of chromium hydroxide is 0.30 or more and 0.90 or less, and the insulating film is It has an innermost layer laminated on the surface, the innermost layer is mainly composed of a resin component containing maleic anhydride-modified polypropylene, and the acid modification rate of the resin component is 0.02% by mass or more and 0.50% by mass or less. be.
  • the conductor is coated with a conductor film containing a trivalent chromium compound including chromium hydroxide and a metal element, so that the electrolyte is generated by hydrolysis of the non-aqueous electrolyte. Peeling at the interface between the conductor and the insulating film caused by corrosion of the conductor by hydrofluoric acid can be suppressed.
  • the innermost layer laminated on the surface of the conductor coating has a resin component containing maleic anhydride-modified polypropylene as a main component, and the acid modification rate of the resin component is 0.02% by mass or more and 0.50% by mass or less.
  • the adhesiveness between the innermost layer and the conductive film is good.
  • the ratio of the mass of chromium atoms per unit area of the chromium hydroxide [mg/m 2 ] to the mass of chromium atoms per unit area of the trivalent chromium compound [mg/m 2 ] on the outermost surface of the conductor coating. is 0.30 or more and 0.90 or less, the conductor coating has a sufficient amount of hydrogen bonds with the maleic anhydride-modified polypropylene in the innermost layer, and the mechanical strength of the conductor coating is good. It is possible to improve the adhesion strength between the film and the insulating film.
  • the outermost surface of the conductive film has a ratio of the mass of chromium atoms per unit area of the chromium hydroxide to the mass of chromium atoms per unit area of the trivalent chromium compound from 0.30 to 0.90. Due to the adhesion of moisture from the atmosphere, the amount of hydroxyl groups on the surface is lower than that of an untreated conductor surface, which is considered to be covered almost 100% with hydroxide. On the other hand, by setting the acid modification rate of the resin component, which is the main component of the innermost layer, to 0.02% by mass or more and 0.50% by mass or less, the hydroxyl groups on the conductor surface can be compensated for. The adhesive strength between films can be further improved. Therefore, the lead wire for a non-aqueous electrolyte battery has excellent resistance to the non-aqueous electrolyte of the non-aqueous electrolyte battery.
  • the mass [mg/m 2 ] ratio of chromium atoms per unit area of the chromium hydroxide to the trivalent chromium compound is the mass of chromium atoms per unit area on the outermost surface of the conductor coating and the mass of chromium atoms per unit area on the outermost surface of the conductor coating. It can be determined from the mass of hydroxyl groups per unit area.
  • the mass of chromium atoms per unit area on the outermost surface of the conductive film is calculated using X-ray Photoelectron Spectroscopy (hereinafter also referred to as "XPS").
  • the above-mentioned “on the outermost surface of the conductive film” refers to the area up to the detection depth that can be measured using the above-mentioned X-ray photoelectron spectroscopy on any surface, specifically, approximately 5 nm in the depth direction from any surface. Indicates the area that has been entered.
  • the main component means a component whose content exceeds 50% by mass.
  • the metal element is nickel, aluminum, copper, or a combination thereof.
  • the conductor film contains nickel, aluminum, copper, or a combination thereof as a metal element, the conductivity of the conductor can be further improved.
  • the conductive film further contains a calcium compound, a fluorine compound, or a combination thereof.
  • the conductive film further contains a calcium compound
  • the lead wire for a non-aqueous electrolyte battery is used in a non-aqueous electrolyte battery, decomposition products of the non-aqueous electrolyte component in the non-aqueous electrolyte battery are generated. Since the stability of the conductor film against corrosion is improved, it can have excellent corrosion resistance.
  • the conductive film further contains a fluorine compound the formation of a stable passivation film is promoted, so that corrosion resistance can be further improved.
  • the acid modification rate of the resin component is 0.10% by mass or more and 0.50% by mass or less.
  • the adhesive strength between the conductor and the insulating film can be further improved.
  • the average thickness of the conductive film is 1 nm or more and 50 nm or less.
  • the conductor coating is 1 nm or more and 50 nm or less, the conductor has good corrosion resistance.
  • the average thickness of the insulating film is 0.05 mm or more and 0.50 mm or less.
  • the gap between the insulating film and the enclosure can be sufficiently filled, and non-water can pass through the insulating film from the atmosphere. It is possible to reduce the amount of water that infiltrates into the electrolyte battery.
  • the average thickness of the innermost layer is 0.01 mm or more and 0.25 mm or less.
  • the adhesion to the conductor is improved, and the amount of moisture that permeates the insulating film from the atmosphere and enters the inside of the non-aqueous electrolyte battery. can be suppressed.
  • the conductor is nickel, nickel plated metal, nickel-phosphorous alloy plated metal, aluminum or aluminum alloy.
  • the conductor is made of nickel, nickel plated metal, nickel-phosphorus alloy plated metal, aluminum or aluminum alloy, it is possible to improve conductivity, potential resistance, etc.
  • the nonaqueous electrolyte battery of the present disclosure includes an enclosure, a plurality of lead wires for the nonaqueous electrolyte battery arranged to extend from the inside of the enclosure to the outside, and a nonaqueous electrolyte. .
  • the non-aqueous electrolyte battery can suppress peeling of the conductor and the insulating film and improve airtightness.
  • FIG. 1 is a perspective view of a lead wire for a non-aqueous electrolyte battery according to an embodiment of the present disclosure.
  • FIG. 2 is a partial cross-sectional view of a lead wire for a non-aqueous electrolyte battery according to an embodiment of the present disclosure.
  • the lead wire 1 for a nonaqueous electrolyte battery has a conductor 3 and one or more layers, and an insulating film that covers at least a part of the outer peripheral surface of the conductor 3. 5.
  • the conductor 3 having one end portion 4a and the other end portion 4b has a conductor coating 9 covering at least a portion of the surface.
  • the insulating film 5 includes an innermost layer 6 laminated on the surface of the conductor 3, a first insulating layer 8 laminated on the outermost surface of the insulating film 5, and a layer laminated on the inner surface of the first insulating layer 8. and a second insulating layer 7.
  • the conductor corresponds to a lead conductor.
  • the conductor 3 is connected to an electrode or the like of a non-aqueous electrolyte battery.
  • the conductor 3 may be made of metal materials such as aluminum, titanium, nickel, copper, aluminum alloys, titanium alloys, nickel alloys, copper alloys, or nickel plating of these metal materials with nickel. Examples include metals, nickel-phosphorus alloy plated metals, and the like. Among these, nickel, nickel plated metal, and nickel-phosphorus alloy plated metal are preferable as the material for forming the conductor 3 connected to the negative electrode of the non-aqueous electrolyte battery. On the other hand, as the material for forming the conductor 3 connected to the positive electrode, aluminum and aluminum alloy are preferable from the viewpoints of potential resistance, high conductivity, and cost.
  • the lower limit of the average thickness of the conductor 3 is preferably 0.10 mm. When the average thickness of the conductor 3 is 0.10 mm or more, a sufficient amount of current can flow for practical use as a battery. Further, the lower limit of the average thickness of the conductor 3 may be further 0.15 mm or 0.20 mm.
  • the upper limit of the average thickness of the conductor 3 is not particularly limited, and can be appropriately set, for example, depending on the capacity of the non-aqueous electrolyte battery.
  • the upper limit of the average thickness is preferably 5.00 mm. When the average thickness of the conductor 3 is 5.00 mm or less, resistance heat generation in the lead wire portion can be suppressed even if the lead wire is rapidly charged and discharged. Moreover, the upper limit of the average thickness of the conductor 3 may further be 4 mm. Note that the "average thickness" of the conductor 3 is the average value of thickness measurements at 10 points. In the following, "average thickness" has the same meaning.
  • the conductor coating 9 covers at least a portion of the surface of the conductor 3.
  • the conductive film 9 contains a trivalent chromium compound including chromium hydroxide and a metal element. Since the conductor 3 is coated with a conductor film containing a trivalent chromium compound containing chromium hydroxide and a metal element, the corrosion resistance of the conductor 3 is improved.
  • the above metal element is preferably nickel, aluminum, copper, or a combination thereof.
  • the conductor film 9 contains nickel, aluminum, copper, or a combination thereof as a metal element, the conductivity of the conductor 3 can be further improved.
  • Lower limit of the ratio of the mass per unit area of chromium [mg/m 2 ] contained in the chromium hydroxide to the mass per unit area [mg/m 2 ] of chromium contained in the trivalent chromium compound on the outermost surface of the conductor coating 9 is 0.30, preferably 0.40. If the above mass ratio is less than 0.30, the conductor coating 9 may not be able to form a sufficient amount of hydrogen bonds with the maleic anhydride-modified polypropylene in the innermost layer 6, and the adhesive strength between the conductor and the insulating film may be insufficient. be.
  • the upper limit of the mass ratio of chromium atoms per unit area of chromium hydroxide to the trivalent chromium compound is 0.90, preferably 0.80. If the mass ratio exceeds 0.90, the mechanical strength of the conductor coating 9 may decrease, and the adhesive strength between the conductor 3 and the insulating film 5 may become insufficient.
  • the conductive film 9 further contains a calcium compound, a fluorine compound, or a combination thereof. Since the conductive film 9 further contains a calcium compound, when the lead wire 1 for a non-aqueous electrolyte battery is used in a non-aqueous electrolyte battery, the non-aqueous electrolyte component in the non-aqueous electrolyte battery can be decomposed. Since the stability of the conductor coating 9 with respect to products is improved, it can have excellent corrosion resistance. When the conductive film 9 further contains a fluorine compound, the formation of a stable passivation film is promoted, so that corrosion resistance can be further improved.
  • Examples of the calcium compound include calcium oxide, calcium hydroxide, calcium carbonate, calcium chromate, calcium chromate dihydrate, anhydrous calcium chromate, and calcium aluminate compounds.
  • Examples of the fluorine compound include calcium fluoride, chromium fluoride, aluminum fluoride, and copper fluoride. Calcium compounds and fluorine compounds in the conductive film 9 can be confirmed by XPS.
  • the lower limit of the average thickness of the conductor film 9 is preferably 1 nm, more preferably 3 nm. When the average thickness of the conductor film 9 is 1 nm or more, sufficient corrosion resistance of the conductor 3 can be obtained.
  • the upper limit of the average thickness of the conductive film 9 is preferably 50 nm, more preferably 20 nm. When the average thickness of the conductive film 9 is 50 nm or less, a decrease in density due to the formation of cracks in the conductive film 9 can be suppressed, and corrosion resistance can be maintained better.
  • the average thickness of the conductor coating 9 can be measured by analyzing the elements present on the surface of the conductor 3 covered with the conductor coating 9 using XPS.
  • the insulating film 5 is used as an insulating film of the lead wire 1 for a non-aqueous electrolyte battery.
  • the insulating film 5 has one or more insulating layers, and is laminated on the outer circumferential surface of the conductor 3 so as to cover at least a part of the outer circumferential surface of the conductor 3. Since the insulating film 5 has one or more insulating layers 3, various functions can be provided depending on the purpose of the lead wire 1 for a non-aqueous electrolyte battery.
  • the lead wire 1 for a non-aqueous electrolyte battery of this embodiment includes an insulating film 5 having three insulating layers 3.
  • the lower limit of the average thickness of the insulating film 5 is preferably 0.05 mm. Since the average thickness of the insulating film 5 is 0.05 mm or more, the gap between the insulating film 5 and the enclosure 11 caused by a step equal to the thickness of the conductor 3 can be reliably filled with the insulating film 5. Can be sealed. Further, the lower limit of the average thickness of the insulating film 5 may be further 0.08 mm or 0.10 m. On the other hand, the upper limit of the average thickness of the insulating film 5 is preferably 0.50 mm.
  • the average thickness of the insulating film 5 is 0.50 mm or less, the amount of water that permeates the insulating film 5 from the atmosphere and enters the inside of the non-aqueous electrolyte battery 10 is reduced, and the non-aqueous electrolyte battery is Deterioration can be suppressed. Further, the upper limit of the average thickness of the insulating film 5 may be further 0.40 mm or 0.30 mm.
  • the average thickness of the insulating film 5 is the average value of thickness measurements at 10 points on the surface with the largest area among the outer peripheral surfaces of the insulating film 5.
  • the insulating film 5 includes an innermost layer 6 laminated on the surface of the conductor 3, a first insulating layer 8 laminated on the outermost surface of the insulating film 5, and an inner surface of the first insulating layer 8.
  • a second insulating layer 7 is provided.
  • the innermost layer 6 is laminated on the surface of the conductive film 9 . Since the insulating film 5 has the innermost layer 6, corrosion of the conductor 3 can be suppressed.
  • the innermost layer 6 mainly contains a resin component containing maleic anhydride-modified polypropylene (maleic anhydride-modified PP). Since the innermost layer 6 mainly contains a resin component containing maleic anhydride-modified polypropylene, it has good adhesion to the conductor coating 9.
  • the lower limit of the acid modification rate of the resin component is 0.02% by mass, preferably 0.10% by mass.
  • the adhesiveness between the innermost layer 6 and the conductive film 9 can be improved, and sufficient resistance to non-aqueous electrolytes can be obtained.
  • the upper limit of the acid modification rate of the resin component is 0.50% by mass, preferably 0.40% by mass.
  • the maleic anhydride modified group can suppress corrosion of the conductor 3 and improve corrosion resistance.
  • the above acid modification rate is calculated from the mass of the carboxy group measured from the peak area of 1710 cm -1 by infrared spectroscopic transmission method (transmission FT-IR), and from the average thickness of the six innermost layers based on an appropriate calibration curve. Calculated by conversion.
  • the melting point of the maleic anhydride-modified polypropylene is preferably 130°C or more and 170°C or less, more preferably 130°C or more and 150°C or less.
  • the melting point of the maleic anhydride-modified polypropylene is less than 130°C, there is a risk that the heat resistance will decrease.
  • the melting point of the maleic anhydride-modified polypropylene exceeds 170°C, the amount of heat required to melt the maleic anhydride-modified polypropylene is large, so it cannot be sufficiently melted, and the innermost layer 6 is not sufficiently melted against the conductor 3. Otherwise, proper adhesion may not be obtained.
  • the lower limit of the content of maleic anhydride-modified polypropylene in the innermost layer 6 is preferably 0.1% by mass, more preferably 0.5% by mass. If the content of maleic anhydride-modified polypropylene is less than 0.1% by mass, there is a risk that practically sufficient material properties may not be obtained.
  • the resin component may contain a thermoplastic resin other than maleic anhydride-modified polypropylene as long as the effects of the present disclosure are not impaired.
  • thermoplastic resins other than maleic anhydride-modified polypropylene include polyolefins such as polypropylene and polyethylene.
  • the innermost layer 6 may contain other known additives. Examples of known additives include antioxidants, flame retardants, tackifiers, lubricants, fillers, crystallization promoters, colorants, and the like.
  • the lower limit of the average thickness of the innermost layer 6 is preferably 0.01 mm. When the average thickness of the innermost layer 6 is 0.01 mm or more, sufficient adhesion to the conductor 3 can be obtained. Further, the lower limit of the average thickness of the innermost layer 6 may be 0.02 mm or 0.03 mm. On the other hand, the upper limit of the average thickness of the innermost layer 6 is preferably 0.25 mm. Since the average thickness of the innermost layer 6 is 0.25 mm or less, the amount of moisture that permeates the insulating film 5 from the atmosphere and enters the inside of the non-aqueous electrolyte battery can be reduced, and deterioration of the battery can be suppressed.
  • the upper limit of the average thickness of the innermost layer 6 may be 0.22 mm or 0.20 mm.
  • the average thickness of the innermost layer 6 is the average value of thickness measurements at 10 points on the surface with the largest area among the outer peripheral surfaces of the innermost layer 6.
  • the first insulating layer 8 is disposed farthest from the conductor 3 and is made of thermoplastic resin.
  • the first insulating layer 8 is laminated on the outermost surface of the insulating film 5, and is laminated on the surface of the second insulating layer 7.
  • the first insulating layer 8 is preferably composed mainly of a resin that is easily melted at the heat-sealing temperature when the opening of the enclosure is heat-sealed (thermal fusion), and more preferably is composed mainly of a polyolefin. .
  • polyolefins examples include polypropylene, polyethylene, and derivatives thereof. More specifically, homopolypropylene, block polypropylene, random polypropylene, low-crystalline polypropylene, low-density polyethylene, linear low-density polyethylene, low-crystalline ethylene-propylene copolymer, low-crystalline ethylene-butylene copolymer, Examples include combinations of low crystallinity ethylene-octene copolymers, low crystallinity propylene-ethylene copolymers, and the like.
  • the first insulating layer 8 may contain a plurality of resins.
  • polypropylene is preferable, and as the polypropylene, random polypropylene having a melting point of 120° C. or more and 155° C. or less and an MFR of 3 g/10 minutes or more and 15 g/10 minutes or less is more preferable.
  • the polyolefin is random polypropylene, there is an advantage that adhesiveness between the second insulating layer 7 and the innermost resin layer of the enclosure can be sufficiently exhibited.
  • the lower limit of the polyolefin content in the first insulating layer 8 is preferably 70% by mass. When the polyolefin content is less than 70% by mass, there is a risk that practically sufficient material properties cannot be obtained. Further, the lower limit of the polyolefin content in the first insulating layer 8 may be further 80% by mass, 90% by mass, or 100% by mass.
  • the first insulating layer 8 may contain a thermoplastic resin other than the polyolefin described above as long as the effects of the present disclosure are not impaired.
  • the first insulating layer 8 may contain other known additives as long as the effects of the present disclosure are not impaired.
  • known additives include antioxidants, flame retardants, tackifiers, lubricants, fillers, crystallization promoters, colorants, and the like.
  • the lower limit of the average thickness of the first insulating layer 8 is preferably 25 ⁇ m. If the average thickness of the first insulating layer 8 is less than 25 ⁇ m, the first insulating layer 8 may not have sufficient strength. Further, the lower limit of the average thickness of the first insulating layer 8 may be further 30 ⁇ m or 40 ⁇ m. On the other hand, the upper limit of the average thickness of the first insulating layer 8 is preferably 250 ⁇ m. If the average thickness of the first insulating layer 8 exceeds 250 ⁇ m, the amount of water that permeates the insulating film 5 from the atmosphere and enters the inside of the non-aqueous electrolyte battery increases, which may accelerate deterioration of the battery.
  • the average thickness of the first insulating layer 8 is the average value of thickness measurements at 10 points on the surface with the largest area among the outer peripheral surfaces of the first insulating layer 8. .
  • the insulating film 5 may have a second insulating layer 7 between the first insulating layer 8 and the innermost layer 6.
  • the second insulating layer 7 is laminated on the inner surface of the first insulating layer 8. It is preferable that the second insulating layer 7 contains a crosslinked polyolefin or a polyolefin having a higher melting point than the innermost layer 6. Since the second insulating layer 7 contains crosslinked polyolefin or a polyolefin resin having a higher melting point than the innermost layer 6, it is difficult to melt at the heat sealing temperature when the opening of the enclosure is heat-sealed, and the metal of the enclosure is Short circuits between layers and conductors can be suppressed.
  • polystyrene resin examples include polypropylene, polyethylene, derivatives thereof, and the like.
  • high melting point polyolefin high melting point polypropylene with a melting point of 155° C. or higher is preferable, and homopolypropylene, block polypropylene, thermoplastic olefin elastomer (TPO), etc. are particularly preferable.
  • the second insulating layer 7 may contain thermoplastic resins other than the above-mentioned crosslinked polyolefin, or may contain other known additives, as long as the effects of the present disclosure are not impaired.
  • known additives include antioxidants, flame retardants, tackifiers, lubricants, fillers, crystallization promoters, colorants, and the like.
  • the lower limit of the average thickness of the second insulating layer 7 is preferably 25 ⁇ m. If the average thickness of the second insulating layer 7 is less than 25 ⁇ m, the second insulating layer 7 may not have sufficient strength. Further, the lower limit of the average thickness of the second insulating layer 7 may be further 30 ⁇ m or 40 ⁇ m. On the other hand, the upper limit of the average thickness of the second insulating layer 7 is preferably 250 ⁇ m. When the average thickness of the second insulating layer 7 exceeds 250 ⁇ m, there is a possibility that the amount of water that permeates the insulating film 5 from the atmosphere and enters the inside of the non-aqueous electrolyte battery increases.
  • the average thickness of the second insulating layer 7 is the average value of thickness measurements at 10 points on the surface with the largest area among the outer peripheral surfaces of the second insulating layer 7. .
  • the method for manufacturing the lead wire for a non-aqueous electrolyte battery is not particularly limited, and may be manufactured by a known method.
  • a chemical conversion treatment (chromate treatment) is performed on at least a portion of the surface of the conductor using a treatment liquid in the following manner to coat the conductor with a conductor film.
  • a chemical conversion treatment chromate treatment
  • the front, back, and side surfaces of the conductor are degreased.
  • oily components may adhere to its surface, and the degreasing described above is performed to remove these oily components and oil.
  • the degreasing treatment can be performed by coating or immersing in an organic solvent, surfactant, acid, or alkaline solution.
  • the metal surface is subjected to chemical conversion treatment using a solution containing chromate as a main component.
  • Acidic compounds used for degreasing include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, and sulfamic acid, citric acid, gluconic acid, oxalic acid, tartaric acid, formic acid, hydroxyacetic acid, and EDTA (ethylene diamine tetra acetic acid (ethylenediaminetetraacetic acid), ammonium thioglycolate, and the like.
  • inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, and sulfamic acid
  • citric acid gluconic acid
  • oxalic acid tartaric acid
  • formic acid formic acid
  • hydroxyacetic acid formic acid
  • EDTA ethylene diamine tetra acetic acid (ethylenediaminetetraacetic acid), ammonium thioglycolate, and the like
  • alkaline compounds include sodium hydroxide (NaOH), sodium carbonate (Na 2 CO 3 ), sodium bicarbonate (NaHCO 3 ), sulfur salt (Na 2 SO 4 .10H 2 O), and sodium sesquicarbonate (Na 2 CO 3 ).
  • Sodium salts such as 3.NaHCO 3.2H 2 O), sodium orthosilicate (2Na 2 O.SiO 2 , moisture 10% to 40%), sodium metasilicate (2Na 2 O.SiO 2.9H 2 O), etc.
  • Silicates monobasic sodium phosphate (NaH 2 PO 4 ), sodium pyrophosphate (Na 4 P 2 O 7 ), dibasic sodium phosphate (Na 2 HPO 4 ), sodium hexametaphosphate ⁇ (NaPO 3 ) 6 ⁇ , phosphates such as trisodium phosphate (Na 3 PO 4 ), and the like.
  • Chemical conversion treatment methods include immersing the conductor in the treatment liquid, spraying the conductor with the treatment liquid, and coating the conductor with the treatment liquid using a roll coating method. Then, the front and back surfaces, side surfaces, etc. of the conductor are subjected to chemical conversion treatment. In the chemical conversion treatment, at least the covered portion of the insulating film may be treated, but it is desirable to treat the entire circumference of the conductor using a dipping method, a shower method, a roll coating method, or the like.
  • an aqueous solution containing 5.0 g/L of chromium chloride hexahydrate and 170 g/L of potassium formate is used as the treatment liquid for the chemical conversion treatment.
  • the above treatment solution is applied to the conductor by cathodic electrolysis at 45° C. and a current density of 10 A/dm 2 for 30 seconds. Next, after drying, it is baked at a heating temperature of 100° C. or more and 300° C. or less to form a conductive film.
  • the method for manufacturing the insulating film is not particularly limited.
  • the forming resin composition containing the respective resin components and additives of each insulating layer is mixed using a known mixing device such as an open roll, a pressure kneader, a single-screw mixer, a twin-screw mixer, or the like.
  • each film-like insulating layer can be produced by extrusion molding such as T-die molding or inflation molding. Then, each insulating layer is superimposed and thermally laminated and bonded using a hot roll.
  • a plurality of insulating layers can be formed simultaneously using an inflation method using coextrusion or a T-die method.
  • an extrusion lamination method can be used in which a molten resin is laminated on a film formed in a single layer.
  • the film-like insulating film is cut to a predetermined size and is bonded to both sides of the conductor using heat and pressure using a thermocompression bonding method, thereby covering at least a portion of the outer peripheral surface of the conductor.
  • the insulating layer can be produced not only by extrusion molding but also by injection molding. In injection molding, the peripheral surface of the conductor can be covered by injecting resin after the conductor is mounted in a mold, and two-color molding can be used when forming multiple layers.
  • the lead wire for a non-aqueous electrolyte battery has excellent resistance to the non-aqueous electrolyte of a non-aqueous electrolyte battery.
  • the non-aqueous electrolyte battery 10 includes the aforementioned non-aqueous electrolyte battery lead wire 1 and a non-aqueous electrolyte.
  • Examples of nonaqueous electrolyte batteries include secondary batteries such as lithium ion batteries.
  • FIG. 3 is a perspective view showing an example of a non-aqueous electrolyte battery including the lead wire for the non-aqueous electrolyte battery.
  • FIG. 4 is a partial cross-sectional view schematically showing one embodiment of a non-aqueous electrolyte battery.
  • the non-aqueous electrolyte battery (non-aqueous electrolyte secondary battery) 10 shown in FIGS. 3 and 4 includes a plate-shaped positive electrode, a plate-shaped negative electrode, a non-aqueous electrolyte, an enclosure container 11, and a plurality of Specifically, it includes two lead wires 1 for a non-aqueous electrolyte battery.
  • the lead wire 1 for a non-aqueous electrolyte battery is the aforementioned lead wire for a non-aqueous electrolyte battery.
  • the insulating film 5 has the innermost layer 6, the second insulating layer 7, and the first insulating layer 8, as described above.
  • the nonaqueous electrolyte battery 10 has a substantially rectangular enclosure 11 and two nonaqueous electrolyte battery lead wires 1 extending from the inside of the enclosure 11 to the outside.
  • the conductor 3 and the enclosure 11 are connected through the insulating film 5 at the seal portion 13 of the enclosure 11.
  • the enclosure container 11 is a container that contains a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte in a sealed state.
  • a positive electrode and a negative electrode are stacked with a separator in between to form a stacked electrode group.
  • This laminated electrode group and the non-aqueous electrolyte are housed in an enclosure 11 in a sealed state.
  • the laminated electrode group is immersed in the electrolytic solution.
  • the enclosure 11 is formed from a sheet body, as will be described later.
  • the seal portion 13 around the two sheet bodies or one folded sheet body is heat-sealed to be in a sealed state.
  • one end 4a of the conductor 3 of the lead wire 1 for non-aqueous electrolyte batteries is exposed from the enclosure 11, and the other The end portion 4b is arranged so as to be connected to the positive electrode within the enclosure container 11.
  • the other non-aqueous electrolyte battery lead wire 1 is arranged so that one end 4a of the conductor 3 is exposed from the enclosure 11 and the other end 4b is connected to the negative electrode inside the enclosure 11.
  • the enclosure 11 is not stacked on both end portions of the conductor 3, that is, the one end portion 4a and the other end portion 4b.
  • One end 4a of the conductor 3 is exposed from the enclosure 11.
  • an internal connection lead wire 14 is connected to the other end 4b of the conductor 3 of the nonaqueous electrolyte battery lead wire 1 on the positive electrode side through a solder portion 15, and by this internal connection lead wire 14, Connected to a positive electrode (not shown).
  • the other end 4b of the conductor 3 of the lead wire 1 for a non-aqueous electrolyte battery on the negative electrode side is connected to an internal connection lead wire 14 via a solder portion 15. is connected to a negative electrode (not shown).
  • the above-mentioned positive electrode and negative electrode are typically laminates in which an active material layer containing an active material is laminated on the surface of a current collector such as metal foil.
  • the shape of the positive electrode and the negative electrode is usually plate-like, but may be in a shape other than plate-like.
  • the separator is usually an insulating and porous film. This separator is impregnated with a non-aqueous electrolyte.
  • the nonaqueous electrolyte includes a nonaqueous solvent and an electrolyte salt dissolved in the nonaqueous solvent.
  • the enclosure 11 is composed of a sheet body in which an innermost resin layer 27, a metal layer 25, and an outermost resin layer 26 are laminated in this order. Then, the sealed container 11 is formed by overlapping two sheet bodies and heat-sealing three sides other than the side through which the conductor passes, thereby forming a sealed portion 13. Further, in the sealing portion 13, the conductor 3 of each lead wire 1 for a non-aqueous electrolyte battery is adhered to the enclosure 11 with the insulating film 5 interposed therebetween. In this portion, the innermost resin layer 27 of the enclosure 11 and the first insulating layer 8 of each lead wire 1 for a non-aqueous electrolyte battery are thermally fused.
  • the innermost resin layer 27 is directly laminated on the inner surface of the metal layer 25.
  • an insulating resin that does not dissolve in the non-aqueous electrolyte and melts when heated.
  • the innermost resin layer 27 for example, polyolefin, acid-modified polyolefin, acid-modified styrene elastomer, etc. can be used. Among these, polypropylene is preferred as the innermost resin layer 27.
  • the average thickness of the innermost resin layer 27 is preferably about 10 ⁇ m to 500 ⁇ m.
  • the metal layer 25 has functions such as improving the strength of the enclosure 11 and preventing water vapor, oxygen, light, etc. from entering the inside of the battery.
  • Metal layer 25 is formed from metal such as aluminum foil.
  • the metal layer 25 has metal as a main component. Examples of this metal include aluminum, copper, stainless steel, and titanium, with aluminum being particularly preferred.
  • the metal layer 25 is substantially made of metal, but may contain additives other than metal.
  • the metal layer 25 is in the form of a film, preferably made of metal foil, and more preferably made of aluminum alloy foil. Further, the average thickness of the metal layer 25 is preferably about 10 ⁇ m to 50 ⁇ m.
  • the outermost resin layer 26 has a function of protecting the outer surface of the metal layer 25 and an insulating function.
  • the outermost resin layer 26 located on the outside of the enclosure usually has resin as its main component as an insulating material.
  • the resin forming the outermost resin layer 26 include polyethylene terephthalate (PET), polyamide, polyester, polyolefin, epoxy resin, acrylic resin, fluororesin, polyurethane, silicone resin, phenol resin, polyetherimide, polyimide, and the like. Examples include mixtures and copolymers of .
  • the outermost resin layer 26 may be composed of a plurality of layers with an adhesive layer containing, for example, polyethylene terephthalate or polyamide interposed therebetween. Further, the average thickness of the outermost resin layer 26 is preferably about 10 ⁇ m to 50 ⁇ m.
  • one end of the non-aqueous electrolyte battery lead wire 1, that is, one end portion 4a of the conductor 3, is arranged in a state exposed from the enclosure 11, and the one end 4a of the conductor 3 is exposed from the enclosure 11. It is sealed.
  • the lead wire 1 for a non-aqueous electrolyte battery is arranged so that the innermost resin layer of the enclosure 11 and the insulating film 5 of the lead wire 1 for a non-aqueous electrolyte battery are in direct contact.
  • the innermost resin layer 27 in the seal portion 13 of the enclosure 11 and the first insulating layer 8 of the lead wire 1 for a non-aqueous electrolyte battery are heat fused.
  • the positive electrode, negative electrode, and separator which are the laminated electrode group immersed in the non-aqueous electrolyte, can be sealed in the enclosure 11.
  • a method for manufacturing a non-aqueous electrolyte battery according to an embodiment of the present disclosure can be appropriately selected from known methods.
  • the method for manufacturing the nonaqueous electrolyte battery includes, for example, a step of preparing lead wires for the nonaqueous electrolyte battery, a step of preparing a laminated electrode group, a step of preparing a nonaqueous electrolyte, and a step of preparing the nonaqueous electrolyte battery.
  • the method includes a step of accommodating a laminated electrode group to which an electrolyte battery lead wire is connected and a non-aqueous electrolyte in an enclosure.
  • the non-aqueous electrolyte battery can suppress peeling of the conductor and the insulating film and improve airtightness.
  • the lead wire for a nonaqueous electrolyte battery was provided with an insulating film having a three-layer structure having an innermost layer, a second insulating layer, and a first insulating layer.
  • the line may include a two-layer insulating film that does not include the second insulating layer.
  • the lead wire for a non-aqueous electrolyte battery may include an insulating film having a multilayer structure having one or more intermediate layers inside the second insulating layer.
  • the substrate after acid activation was washed with running water. Next, nickel amidosulfate tetrahydrate (350 g/L), nickel chloride hexahydrate (30 g/L), and boric acid (30 g/L) were mixed to obtain a nickel plating solution.
  • the base material after acid activation was immersed in a 50° C. nickel plating solution, and plating was performed at a current density of 5.0 A/dm 2 for 120 seconds.
  • a lead conductor made of nickel-plated copper (nickel-plated metal) was obtained by washing the base material after plating with running water.
  • Chromium chloride hexahydrate (5.0 g/L) and potassium formate (170 g/L) were mixed with pure water to obtain a surface treatment liquid.
  • the lead conductor was immersed in a surface treatment solution at 45° C., and cathode electrolysis was performed at a current density of 10 A/dm 2 for 30 seconds.
  • the lead conductor after cathodic electrolysis was washed with running water and dried in a constant temperature bath at 100° C. for 180 seconds to obtain a lead conductor having a conductor coating.
  • the ratio of the mass per unit area of chromium [mg/m 2 ] contained in the chromium hydroxide to the mass per unit area [mg/m 2 ] of chromium contained in the trivalent chromium compound on the outermost surface of this conductor coating is It was 0.40.
  • a two-layer insulating film including an innermost layer and a first insulating layer was fabricated.
  • resin compositions for the innermost layer and the first insulating layer were prepared using a mixing device.
  • Second Insulating Layer As a material for the resin composition of the first insulating layer, random polypropylene: "Prime Polypro F227D" manufactured by Prime Polypro Co., Ltd. (MFR 7 g/10 minutes, melting point 140° C.) was used. (3) Preparation of insulating film Next, using a coat hanger type two-layer T-die film forming machine equipped with two single-screw extruders, the innermost layer resin composition was applied to the first extruder, The first insulating layer resin compositions are each put into a second extruder and coextruded to obtain a two-layer insulating film laminated in the order of innermost layer resin composition/first insulating layer resin composition. Ta. The average thickness of the innermost layer was 50 ⁇ m, and the average thickness of the first insulating layer was 100 ⁇ m.
  • Test No. 3 In the production of the insulating film, 100 parts by mass of "Prime Polypro F227D” manufactured by Prime Polypro Co., Ltd. as random polypropylene and "POLYBOND 3000” manufactured by SIIgroup Co. as maleic anhydride modified polypropylene were used as materials for the innermost layer resin composition. Test No. 1 was used except that 15 parts by mass was used to obtain random PP with an acid modification rate of 0.18% by mass. A lead wire for a non-aqueous electrolyte battery was obtained in the same manner as in Example 1.
  • Test No. 5 In the production of the insulating film, 100 parts by mass of "Prime Polypro F227D” made by Prime Polypro Co., Ltd. as random polypropylene and "POLYBOND 3000” made by SIIgroup Co. as maleic anhydride modified polypropylene were used as the materials for the innermost layer resin composition. Test No. 1 was used except that 50 parts by mass was used to obtain random PP with an acid modification rate of 0.60 mass%. A lead wire for a non-aqueous electrolyte battery was obtained in the same manner as in Example 1.
  • the ratio of the mass per unit area of chromium contained in the above chromium hydroxide to the mass per unit area of chromium contained in the above trivalent chromium compound on the outermost surface of the conductor coating No. 1 except that a lead conductor having a conductor coating having a conductor coating of 0.60 was obtained.
  • a lead wire for a non-aqueous electrolyte battery was obtained in the same manner as in 3.
  • chromium chloride hexahydrate (5.0 g/L), potassium formate (170 g/L), and potassium fluoride (5.0 g/L) were mixed with pure water to obtain a surface treatment solution.
  • Ta. The lead conductor was immersed in a surface treatment solution at 45° C., and cathode electrolysis was performed at a current density of 10 A/dm 2 for 10 seconds.
  • the ratio of the mass per unit area of chromium contained in the above chromium hydroxide to the mass per unit area of chromium contained in the above trivalent chromium compound on the outermost surface of the conductor coating No. 1, except that a lead conductor having a conductor coating having a coefficient of 0.40 was obtained.
  • a lead wire for a non-aqueous electrolyte battery was obtained in the same manner as in 3.
  • the above-mentioned hydroxide is removed with respect to the mass per unit area of chromium contained in the above-mentioned trivalent chromium compound on the outermost surface of the conductor coating.
  • No. 1 except that a lead conductor having a conductor coating having a mass ratio of chromium to unit area of chromium of 0.20 was obtained.
  • a lead wire for a non-aqueous electrolyte battery was obtained in the same manner as in 2.
  • the maleic anhydride modification rate of polypropylene is determined based on the mass of the carboxy group measured from the peak area of 1710 cm -1 by infrared spectroscopic transmission method using "Nicolet 8700” manufactured by Thermo Fisher, based on an appropriate calibration curve. It was calculated by converting from the average thickness of the inner layer.
  • the conductor is coated with a conductor film containing a trivalent chromium compound including chromium hydroxide and a metal element, and is laminated on the surface of the conductor film.
  • Test No. 1 in which the innermost layer of the insulating film is mainly composed of a resin component containing maleic anhydride-modified polypropylene, and the acid modification rate of the resin component is 0.02% by mass or more and 0.50% by mass or less. 2 ⁇ Test No. 4.
  • Test No. 9 ⁇ Test No. 11 and test no. No. 13 had no peeling at the interface between the conductor and the insulating film in the peeling test, and had good resistance to the non-aqueous electrolyte.
  • the acid modification rate of the resin component which is the main component of the innermost layer, was less than 0.02% by mass. 1.
  • Test No. 1 in which the acid modification rate of the resin component exceeds 0.50% by mass. 5.
  • Test No. 5 in which the ratio of the mass per unit area of chromium contained in chromium hydroxide to the mass per unit area of chromium contained in the trivalent chromium compound on the outermost surface of the conductor coating exceeds 0.90. 7
  • Test No. 7 in which the ratio of the mass per unit area of chromium contained in chromium hydroxide to the mass per unit area of chromium contained in the trivalent chromium compound is less than 0.30. 8 and test no.
  • peeling was observed at the interface between the conductor and the insulating film in the peel test, and the resistance to the non-aqueous electrolyte was poor.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Connection Of Batteries Or Terminals (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
PCT/JP2022/033901 2022-09-09 2022-09-09 非水電解液電池用リード線及び非水電解液電池 Ceased WO2024053093A1 (ja)

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CN202280099506.5A CN119790542A (zh) 2022-09-09 2022-09-09 非水电解液电池用引线以及非水电解液电池
KR1020257006798A KR20250038806A (ko) 2022-09-09 2022-09-09 비수 전해액 전지용 리드선 및 비수 전해액 전지
JP2024545402A JPWO2024053093A1 (https=) 2022-09-09 2022-09-09
US19/109,607 US20260100487A1 (en) 2022-09-09 2022-09-09 Nonaqueous electrolyte solution battery lead wire and nonaqueous electrolyte solution battery

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EP4708426A1 (en) * 2024-08-26 2026-03-11 Flexion Co., Ltd Lead tab with improved welding performance
EP4708427A1 (en) * 2024-08-26 2026-03-11 Flexion Co., Ltd Lead tab with improved welding performance
EP4708428A1 (en) * 2024-08-26 2026-03-11 Flexion Co., Ltd Lead tab with improved adhesion

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JP2014225378A (ja) * 2013-05-16 2014-12-04 株式会社日立製作所 タブリード用シール材、タブリードおよびリチウムイオン二次電池
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JP3505905B2 (ja) 1996-03-29 2004-03-15 住友電気工業株式会社 非水電解質電池
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JP2014225378A (ja) * 2013-05-16 2014-12-04 株式会社日立製作所 タブリード用シール材、タブリードおよびリチウムイオン二次電池
JP2016184494A (ja) * 2015-03-26 2016-10-20 Ｊｘ金属株式会社 フィルム外装電池用タブリード材料及びその製造方法
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EP4708426A1 (en) * 2024-08-26 2026-03-11 Flexion Co., Ltd Lead tab with improved welding performance
EP4708427A1 (en) * 2024-08-26 2026-03-11 Flexion Co., Ltd Lead tab with improved welding performance
EP4708428A1 (en) * 2024-08-26 2026-03-11 Flexion Co., Ltd Lead tab with improved adhesion

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