WO2000072388A1 - Method for forming protective coating for cell safety valve device, cell safety valve device covered with protective coating, cell sealing plate comprising the same, and closed cell comprising the same - Google Patents

Method for forming protective coating for cell safety valve device, cell safety valve device covered with protective coating, cell sealing plate comprising the same, and closed cell comprising the same Download PDF

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Publication number
WO2000072388A1
WO2000072388A1 PCT/JP2000/003322 JP0003322W WO0072388A1 WO 2000072388 A1 WO2000072388 A1 WO 2000072388A1 JP 0003322 W JP0003322 W JP 0003322W WO 0072388 A1 WO0072388 A1 WO 0072388A1
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WO
WIPO (PCT)
Prior art keywords
safety valve
battery
hole
valve element
sealing plate
Prior art date
Application number
PCT/JP2000/003322
Other languages
French (fr)
Japanese (ja)
Inventor
Hiroaki Kawamura
Yoshihiko Isobe
Akira Kaneko
Masayoshi Fujinaka
Kunio Nishimura
Original Assignee
Toyo Kohan Co.,Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Kohan Co.,Ltd. filed Critical Toyo Kohan Co.,Ltd.
Priority to AU49484/00A priority Critical patent/AU4948400A/en
Publication of WO2000072388A1 publication Critical patent/WO2000072388A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/30—Arrangements for facilitating escape of gases
    • H01M50/342—Non-re-sealable arrangements
    • H01M50/3425—Non-re-sealable arrangements in the form of rupturable membranes or weakened parts, e.g. pierced with the aid of a sharp member
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for forming a protective film for a battery safety valve element for preventing corrosion of a metal part of a safety valve element used to prevent the burst of a sealed battery, a battery safety valve element coated with a protective film, and
  • the present invention relates to a sealed battery used.
  • sealed batteries using an alkali metal such as lithium as a positive electrode and a negative electrode have been widely used.
  • a sealed structure is indispensable to prevent the reaction between the alkali metal and the moisture in the atmosphere.However, a completely sealed structure allows the battery to be exposed to high temperatures or charged and discharged. If used improperly, the pressure inside the battery may rise abnormally, causing the battery to burst.
  • a battery sealing plate provided with an explosion-proof function and a safety valve is disclosed to release the internal pressure to the outside of the battery when the pressure inside the battery rises abnormally.
  • 5-84025 discloses a safety valve device for a sealed battery in which a gas vent hole is provided in a positive electrode terminal constituting a battery sealing plate and an explosion-proof metal foil is welded. .
  • a gas vent hole is provided in a positive electrode terminal constituting a battery sealing plate and an explosion-proof metal foil is welded.
  • this battery sealing plate when the pressure inside the battery rises, the explosion-proof metal foil is broken, and the pressure inside the battery is released through a gas vent hole provided in the positive electrode terminal.
  • the electrolyte When filling the battery container with the electrolyte, the electrolyte may scatter and adhere to the outside of the battery container.
  • a non-aqueous electrolyte containing a fluorine compound of lithium is used as a supporting electrolyte as an electrolyte.
  • this non-aqueous electrolyte is used inside a battery container to form a battery container or a safety valve element.
  • the above-mentioned fluorine compound absorbs moisture in the atmosphere to form hydrofluoric acid, and has a strong corrosive property.
  • the present invention relates to a method for forming a protective film for a battery safety valve element for coating a surface of a battery safety valve element on the outside of a battery container to prevent corrosion of metal parts, and a battery safety valve element coated with a protective film.
  • An object of the present invention is to provide a battery sealing plate using the same, and a sealed battery using the same. Disclosure of the invention
  • the safety valve for a battery includes a metal substrate having a through hole, and a metal foil laminated on the substrate so as to close the through hole.
  • An organic resin layer is provided on one side of the element outside the battery container.
  • An organic resin layer is provided on one side of the portion where the through hole is closed, which is outside the battery container.
  • the protective film forming method further comprising: a battery safety valve element including a metal substrate having a through-hole formed therein, and a metal foil laminated on the substrate so as to close the through-hole. And a through-hole of the metal plate of the battery safety valve element and a through-hole of the sealing plate are in contact with a sealing plate for a battery outer can having a through-hole formed therein. After bonding using a bonding means so that the two are bonded to each other, an organic resin layer is provided on one side of the battery safety valve element that is outside the battery container.
  • the through-hole of the metal substrate and the through-hole of the sealing plate are in contact with each other so as to communicate with each other, and the two are adhered to each other around the through-hole of the sealing plate using bonding means.
  • An organic resin layer is provided on one side of the element, which is the outside of the battery container, at a portion where the through hole of the metal foil is closed.
  • organic resin particles are placed on one surface j O of the safety valve element outside the battery container, melted using a heating means, and flowed over the entire surface of the safety valve element. Thereafter, the organic resin layer is provided by cooling and solidifying using a cooling means.
  • the organic resin layer is provided by dissolving and flowing over the entire surface of the safety valve element and then cooling and solidifying using a cooling means.
  • the battery safety valve element comprises a metal substrate having a through hole formed therein, and a metal foil laminated on the substrate so as to close the through hole. And a protective film is coated on one side.
  • the metal foil is a battery safety valve element including a metal substrate having a through hole formed therein, and a metal foil laminated on the substrate so as to close the through hole ⁇ . On one side of the battery container outside the portion closing the through hole, It is characterized by being coated with a protective film.
  • the safety valve element for a battery according to claim 12, wherein the protective film is formed by placing particles of an organic resin on one surface of the safety valve element that is outside a battery container, and dissolving the particles using a heating unit. It is an organic resin layer provided by flowing over the entire surface and then cooling and solidifying using cooling means.
  • An organic resin layer provided by melting using a heating means, flowing over the entire surface of the safety valve element, and then cooling and solidifying using a cooling means.
  • a method of forming a protective film for a safety valve element for a battery according to claim 14 is characterized in that the organic resin particles are polypropylene particles or polyethylene particles.
  • a battery sealing plate according to claim 16 is a battery sealing valve for a battery outer can, in which a battery safety valve element according to any one of claims 10 to 15 is provided with a through hole serving as a valve opening of a safety valve.
  • the plate is brought into contact with the through hole of the metal substrate of the battery safety valve element and the through hole of the sealing plate so as to communicate with each other, and the bonding means is used so that the two are bonded around the through hole of the sealing plate. It is characterized by being attached.
  • the battery sealing plate according to claim 17, further comprising: a battery safety valve element including a metal substrate having a through-hole formed therein, and a metal foil laminated on the substrate so as to close the through-hole.
  • a sealing plate for a battery outer can having a through hole serving as a valve port of all valves is abutted so that the through hole of the metal substrate of the battery safety valve element and the through hole of the sealing plate face each other, and the sealing is performed.
  • a protective film is formed on one side of the battery container of the battery
  • a battery sealing plate according to claim 18 is characterized in that the protective film is formed using the protective film forming method according to any one of claims 6 to 9.
  • an electrode body composed of a positive electrode, a negative electrode, and a separator is accommodated in a battery outer can together with an electrolyte, and an inner periphery of an opening of the battery outer can is provided.
  • An opening of the battery outer can is closed by inserting and supporting the battery sealing plate according to any one of claims 16 to 19.
  • FIG. 1 is a schematic sectional view showing an example of a battery safety valve element coated with a protective film of the present invention.
  • FIG. 2 is a schematic sectional view showing another example of the battery safety valve element coated with the protective film of the present invention.
  • FIG. 3 is a schematic sectional view showing another example of the battery safety valve element coated with the protective film of the present invention.
  • Figure 4 shows the bonding of the battery safety valve element of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing an example of a sealed battery plate.
  • FIG. 5 is a schematic cross-sectional view showing another example of the battery sealing plate to which the battery safety valve element of the present invention is adhered.
  • FIG. 6 is a schematic sectional view showing another example of the battery sealing plate to which the battery safety valve element of the present invention is adhered.
  • FIG. 7 (a) is a schematic cross-sectional view showing an example of a battery sealing plate to which a safety valve element for a battery is adhered before coating with a protective film
  • FIG. 7 (b) is a schematic sectional view of the protective film of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing an example of a battery sealing plate to which a battery safety valve element after coating with ⁇ is bonded.
  • FIG. 8 is a schematic sectional view showing another example of the battery sealing plate to which the battery safety valve element of the present invention is adhered.
  • FIG. 1 and 2 are cross-sectional views showing one example of a battery safety valve element coated with the protective film of the present invention.
  • the upper side of the drawing indicates the side outside the battery container.
  • the safety valve element 10 of the present invention is arranged such that the metal substrate 1 having the through hole 4 serving as the valve opening of the safety valve closes the through hole 4 on one side outside the battery container.
  • the protective film 3 is formed on the metal foil 2 on the laminate 5 on which the metal foil 2 is laminated.
  • the safety valve element 10 has a through hole 4 serving as a valve opening of the safety valve.
  • the laminated body 5 on which the foils 2 are laminated is formed on one side of the metal substrate 1 outside the battery container, the side wall of the through hole 4 formed in the metal substrate 1, and the through hole 4 of the metal foil 2.
  • the protective film 3 is formed on the closed part. That is, the protective film 3 covers the entire periphery of the depression formed by the through hole 4 provided in the metal substrate 1 and the metal foil 2, and is continuous with the protective film 3 coated on the metal substrate 1. ing.
  • FIG. 3 is a cross-sectional view showing another example of the battery safety valve element coated with the protective film of the present invention.
  • the safety valve element 10 of the present invention closes the through hole 4 on one side of the metal substrate 1 having the through hole 4 serving as the valve opening of the safety valve on the side inside the battery container.
  • the protective film 3 is formed only on the portion 4 a of the metal foil 2 that closes the through hole 4.
  • the individual safety valve element 10 for a battery according to the present invention is prepared as follows. First, a metal foil 2 is laminated on one surface of a long strip-shaped metal substrate 1 in which a plurality of through holes 4 serving as valve ports are perforated so as to close the through holes 4, and a long strip-shaped laminate 5 is formed. create.
  • the through-hole 4 is usually a circle having a diameter of 1 to 10 mm, but may be an ellipse having a major axis of 1 to 10 mm, or a polygon having a size corresponding to the direct shape of the circle.
  • the shape of the through hole 4 may be a line segment having a constant width (for example, a slit formed of a straight line or a curve) or a through hole having a geometric pattern obtained by combining the above figures.
  • Penetrating The arrangement of the holes 4 is preferably a geometric arrangement such as a lattice arrangement or a staggered arrangement, and the pitch between the through holes 4 is appropriately selected according to the required size of the safety valve member.
  • the through-holes 4 can be formed by using a normal perforation method such as punching and punching of a thin plate formed by cold rolling.
  • the metal substrate 1 and the metal foil 2 in which the through-holes 4 are formed as described above are cooled in a vacuum, for example, by using a method described in Japanese Patent Application Laid-Open No. 122224/1994. That is, after the surfaces of the metal substrate 1 and the metal foil 2 to be laminated are activated by sputtering in an etching chamber, they are cold pressed by a rolling unit provided in a vacuum chamber. Thus, the long strip-shaped laminate 5 of the present invention is produced.
  • a large number of individual battery safety valve elements 10 can be obtained by punching out from the long band-shaped laminate using a punching punch so as to include at least one perforated through hole. it can.
  • an organic resin layer is applied to cover a portion of the metal foil 2 which closes the through hole 4 formed in the metal substrate 1 of the laminated body 5 of the battery safety valve element 10 and is held.
  • Protective coating 3 is applied to cover a portion of the metal foil 2 which closes the through hole 4 formed in the metal substrate 1 of the laminated body 5 of the battery safety valve element 10 and is held.
  • the metal substrate 1 is preferably any one of a steel plate, a stainless steel plate, a copper plate, and an aluminum plate.
  • the plate thickness is usually from 0.03 to 2.0 mm from the viewpoints of strength and economy, and from the viewpoint of easy adhesion to the sealing plate for the battery outer can. More preferably, it is 0.05 to 1.5 mm.
  • the battery safety valve element of the present invention is intended to operate at a low pressure of 30 kgfcm 2 or less, preferably 20 kgf / cm 2 or less. Therefore, the thickness of the metal foil used in the present invention is preferably 5 to 150 m. If it is less than 5 / xm, if it is applied to a safety valve such as a battery, it will be easily broken by impact such as dropping. If the amount exceeds 1 5 0 xm, even using a small metal breaking strength, when applied to the safety valve, 3 0 kgf / cm 2 without fracture at pressures, for the first time breaking it is high load, battery The case itself ruptures, shards are scattered, and the electrolyte blows out and splatters, impairing safety.
  • the metal foil 2 is any one of a steel foil, a stainless steel foil, a copper foil, an aluminum foil, a nickel foil, and a nickel-iron alloy foil. Any metal foil can be used as long as it is stable against the electrolyte and does not corrode or generate a large amount of reaction gas.
  • zinc, lead, brass, bronze, phosphor bronze Metal foils made of copper alloys such as gunmetal and monel, and aluminum alloys such as duralfmin are also applicable.
  • the organic resin layer of the protective film 3 of the safety valve element for a battery shown in FIGS. 1 to 3 above is formed by coating the organic resin layer on the portion covered with the organic resin layer of the metal substrate 1 or the metal foil 2.
  • the particles are placed, melted using a heating means, allowed to flow over the entire surface to be coated, and then cooled and solidified using a cooling means to form the particles.
  • a heating means there can be used, for example, a method of blowing air by a hot air heater or a cool air cooler, and a method of conducting heat from a block by placing it on a heated block or a cooled block.
  • Types of organic resin to be coated include polyolefin resin, polyester resin, polyamide resin, polycarbonate resin, polyvinyl chloride resin, polyurethane resin, paraffin wax, microcrystalline wax, petroleum, wood wax, and polyolefin modified with maleic acid. Resin, unmodified polyolefin resin Can be applied.
  • a granular resin having a particle size of about 0.1 to 2 mm is used, and the number of particles to be placed on the portion to be covered is adjusted according to the area of the portion to be covered.
  • the organic resin those having a low viscosity and high fluidity when melted by heating are preferable.
  • Thermoplastic resins such as resin, polyamide resin, polycarbonate resin, polyvinyl chloride resin, and urethane resin, and waxes such as paraffin wax, microcrystalline silica, petroleum, and wood wax are applicable.
  • polyester resins such as resin, polyamide resin, polycarbonate resin, polyvinyl chloride resin, and urethane resin, and waxes such as paraffin wax, microcrystalline silica, petroleum, and wood wax are applicable.
  • As fats and oils not only polyolefin resins modified with maleic acid to improve adhesion to metals, but also ordinary unmodified polyolefins that do not have adhesion to metals
  • Fin resins can also be suitably used. It is preferable to use paraffin wax as the wax.
  • the thickness of the organic resin layer is preferably 2 to 50 im, more preferably 10 to 30 zm. If it is less than 2 wm, it is difficult to completely cover the metal substrate or sheet metal foil with the organic resin layer
  • the safety valve element 10 of the present invention created as described above has a sealing plate 6 for a battery outer can having a through hole 7 as a valve port of a safety valve as shown in FIGS.
  • the through-hole 4 of the metal substrate 1 of the safety valve element 10 is in contact with the through-hole 7 of the sealing plate 6 for the battery outer can in such a way that the through-hole 7 communicates with the through-hole 7, and an adhesive means such as laser beam welding is used around the through-hole 7.
  • Fig. 4 shows a case where the safety valve element having the structure shown in Fig. 1 is bonded to a sealing plate for a battery outer can.
  • FIGS. 5 and 6 show a case where the safety valve element having the structure shown in FIGS.
  • the bonding means is not limited to the laser one-beam welding method, but may be a necessary bonding method such as a bonding method using an adhesive such as a thermosetting resin-based adhesive, a thermoplastic resin-based adhesive, or a rubber-based adhesive. Any bonding means may be used as long as strength can be obtained.
  • one of the through holes 7 in the sealing plate 6 for the battery outer can is provided with one of the through holes 4 in the metal substrate 1 of the safety valve element 10.
  • a plurality of through holes 4 in the metal substrate 1 of the safety valve element 10 communicate with one of the through holes 7 in the sealing plate 6 for the battery outer can.
  • the sealing plate is preferably any of a steel plate, a stainless steel plate, a copper plate, and an aluminum plate, like the metal substrate.
  • the plate thickness is usually from 0.03 to 2.0 mm, more preferably from 0.05 to L: from the viewpoint of strength and economy, and further from the viewpoint of easy adhesion to the metal substrate. 5 mm.
  • a sealing plate for a battery outer can to which a battery safety valve element coated with a protective film of the present invention is adhered may be prepared as shown in FIGS. 7 (a) and (b). That is, as shown in FIG. 7 (a), a metal substrate 1 having a through-hole 4 and a metal foil 2 laminated on the metal substrate 1 so as to close the through-hole 4 are formed.
  • the battery safety valve element 10 is inserted into a sealing plate 6 for a battery outer can having a through hole 7 serving as a valve opening of the safety valve, and the through hole 4 of the metal substrate 1 of the battery safety valve element 10 and the sealing plate.
  • the through holes 7 of 6 are connected so as to communicate with each other, and the two are adhered to each other around the through hole 7 of the sealing plate 6 by using a laser beam method, and then, as shown in (b) of FIG.
  • the protective film 3 may be provided by forming an organic resin layer on the battery safety valve element 10 including the welded portion. In this way, after the laser one-beam welding, by providing a protective film on the battery safety valve element including the welded part, the metal foil that closes the through hole and the laser beam weld that exposes the metal part are formed. Since it is covered with a protective film, even if a highly corrosive electrolytic solution adheres, the metal parts do not corrode and do not pierce. (Example 4)
  • FIGS. 4 to 7 show that the safety valve element 10 having the same outer diameter as the diameter of the through-hole 7 of the sealing plate 6 is fitted into and adhered to the through-hole 7 of the sealing plate 6, thereby forming a metal for the safety valve element 10.
  • the through hole 4 of the base plate 1 and the through hole 7 of the sealing plate 6 communicate with each other.
  • the safety valve element has an outer diameter larger than the diameter of the through hole 7 of the sealing plate 6. 10 may be superimposed on and contacted with the sealing plate 6 so that the through hole 4 of the metal substrate 1 of the safety valve element 10 and the through hole 7 of the sealing plate 6 communicate with each other.
  • a sealing plate for a battery outer can equipped with a battery safety valve element coated with a protective film of the present invention is stored in an electrode body including a positive electrode, a negative electrode, and a separator together with an electrolyte.
  • the sealed battery of the present invention can be obtained by closing the opening of the battery outer can so as to fit and support the inner periphery of the opening of the battery outer can.
  • the present invention relates to a battery safety valve element comprising a metal substrate having a through-hole formed therein and a metal foil laminated on the substrate so as to close the through-hole, on one side which is outside the battery container.
  • a method for forming a protective film for a battery safety valve element comprising providing an organic resin layer, and a protective film for a battery safety valve element prepared using these methods.
  • the present invention provides a battery safety valve element as described above, wherein a battery safety canister is provided with a through-hole formed in a metal substrate of a battery safety canister and a through-hole of the sealing plate.
  • the battery sealing plate is abutted so that the holes are opposed to each other, and is bonded by using an adhesive means so that the two are bonded around the through hole of the sealing plate, and a positive electrode,
  • the opening of the battery outer can is closed by inserting and supporting the electrode body composed of the negative electrode and the separator into the inner periphery of the opening of the battery outer can housed together with the electrolytic solution.
  • the sealed battery using the sealing plate of the present invention contains a fluorine compound of lithium as a supporting electrolyte, and does not corrode the metal material constituting the battery container and the safety valve element inside the battery container.
  • the fluorine compound absorbs moisture in the atmosphere to form hydrofluoric acid, and the highly corrosive non-aqueous electrolyte scatters, causing the non-aqueous electrolyte to scatter outside the battery container, especially on the metal foil of the safety valve element Even if it adheres, the thin metal foil does not pierce due to corrosion due to the presence of the protective film on the metal foil.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Gas Exhaust Devices For Batteries (AREA)

Abstract

A method for applying a protective coating on a surface of a safety valve device being part of the outer surface of a cell case so as to prevent corrosion of metallic part of the safety valve device, a cell safety valve device covered with a protective coating, cell sealing plate comprising the same, and a closed cell are disclosed. The safety valve device comprises a metallic base where a through hole is made and a metallic foil so provided on the base as to close the through hole. The safety valve device (hereinafter referred to as 'safety valve device comprising a metallic base and a metallic foil') is provided with an organic resin layer on one side serving as part of the outer surface of the cell case. Alternatively, the safety valve device comprising a metallic base and metallic foil is placed in contact with a sealing plate having a through hole therein serving as a valve hole in such a way that the through hole of the metallic base communicates with the through hole of the sealing plate and joined around the through hole of the sealing plate to the sealing plate by using adhesive means, and an organic resin layer is formed on one side of the safety valve device serving as part of the outer surface of the cell case, allowing the organic resin layer to serve as a protective coating of the cell safety valve device.

Description

明 細 書 電池用安全弁素子の保護皮膜形成方法、 保護皮膜を被覆した電池用安全弁素子、 それを用いた電池用封口板およびそれを用いた密閉型電池 技術分野  Description Method of forming protective film for battery safety valve element, battery safety valve element coated with protective film, battery sealing plate using the same, and sealed battery using the same
本発明は、 密閉型電池の破裂を防止するために用いられる安全弁素子の金属部 分の腐食を防止する電池用安全弁素子の保護皮膜形成方法、 保護皮膜を被覆した 電池用安全弁素子、 およびそれを用いた密閉型電池に関する。 背景技術  The present invention relates to a method for forming a protective film for a battery safety valve element for preventing corrosion of a metal part of a safety valve element used to prevent the burst of a sealed battery, a battery safety valve element coated with a protective film, and The present invention relates to a sealed battery used. Background art
近年、 正極および負極としてリチウムなどのアルカリ金属を使用する密閉型電 池が広く用いられるようになってきている。 これらの電池においては、 アルカリ 金属と大気中の水分との反応を防止するために、 密閉構造とすることが不可欠で あるが、 完全密閉構造とすることにより、 高温にさらされたり、 充放電時に使用 方法を誤ったりすると、 電池内部の圧力が異常に上昇し、 電池が破裂することが ある。 この電池内部の圧力が異常に上昇した際に内圧を電池外部に放出させるた めに、 防爆機能や安全弁を備えた電池用の封口板が開示されている。 例えば、 実 開平 5— 8 4 0 2 5公報は、 電池封口板を構成する正極端子にガス抜き孔が設け られ、 防爆用の金属箔が溶接された密閉型電池の安全弁装置を開示している。 こ の電池封口板においては、 電池内部の圧力が上昇した際に防爆用の金属箔が破れ 、 正極端子に設けたガス抜き孔を通して電池内部の圧力が開放される。  In recent years, sealed batteries using an alkali metal such as lithium as a positive electrode and a negative electrode have been widely used. In these batteries, a sealed structure is indispensable to prevent the reaction between the alkali metal and the moisture in the atmosphere.However, a completely sealed structure allows the battery to be exposed to high temperatures or charged and discharged. If used improperly, the pressure inside the battery may rise abnormally, causing the battery to burst. A battery sealing plate provided with an explosion-proof function and a safety valve is disclosed to release the internal pressure to the outside of the battery when the pressure inside the battery rises abnormally. For example, Japanese Utility Model Laid-Open No. 5-84025 discloses a safety valve device for a sealed battery in which a gas vent hole is provided in a positive electrode terminal constituting a battery sealing plate and an explosion-proof metal foil is welded. . In this battery sealing plate, when the pressure inside the battery rises, the explosion-proof metal foil is broken, and the pressure inside the battery is released through a gas vent hole provided in the positive electrode terminal.
電池容器に電解液を充填する際に、 電解液が飛散して電池容器の外部に付着す ることがある。 特にリチウムイオン電池の場合、 電解液として支持電解質として リチウムのフッ素化合物を含む非水電解液が使用されるが、 この非水電解液は電 池容器内部においては電池容器や安全弁素子を構成する金属材料を腐食すること はないが、 大気中においては上記のフッ素化合物が大気中の水分を吸収してフッ 化水素酸となり、 強い腐食性を有するようになる。 このため、 上記のように電解 液が飛散して電池容器の外部、 特に安全弁素子の金属箔に付着すると金属が腐食 され、 薄い金属箔の場合は腐食により穿孔する、 という問題がある。 When filling the battery container with the electrolyte, the electrolyte may scatter and adhere to the outside of the battery container. In particular, in the case of a lithium ion battery, a non-aqueous electrolyte containing a fluorine compound of lithium is used as a supporting electrolyte as an electrolyte. However, this non-aqueous electrolyte is used inside a battery container to form a battery container or a safety valve element. Corroding material However, in the atmosphere, the above-mentioned fluorine compound absorbs moisture in the atmosphere to form hydrofluoric acid, and has a strong corrosive property. For this reason, as described above, when the electrolyte scatters and adheres to the outside of the battery container, especially to the metal foil of the safety valve element, the metal is corroded, and in the case of a thin metal foil, there is a problem that the metal is corroded and perforated.
本発明は、 電池用安全弁素子の電池容器の外側となる面に保護皮膜を被覆して 金属部分の腐食を防止する電池用安全弁素子の保護皮膜の形成方法、 保護皮膜を 被覆した電池用安全弁素子、 それを用いた電池用封口板、 およびそれを用いた密 閉型電池を提供することを課題とする。 発明の開示  The present invention relates to a method for forming a protective film for a battery safety valve element for coating a surface of a battery safety valve element on the outside of a battery container to prevent corrosion of metal parts, and a battery safety valve element coated with a protective film. An object of the present invention is to provide a battery sealing plate using the same, and a sealed battery using the same. Disclosure of the invention
請求項 1の電池用安全弁素子の保護皮膜形成方法は、 貫通孔を穿設した金属基 板と、 前記貫通孔を閉塞するように前記基板上に積層された金属箔とからなる電 池用安全弁素子の電池容器の外側となる片面に、 有機樹脂層を設けることを特徴 とする。  2. The method for forming a protective film of a battery safety valve element according to claim 1, wherein the safety valve for a battery includes a metal substrate having a through hole, and a metal foil laminated on the substrate so as to close the through hole. An organic resin layer is provided on one side of the element outside the battery container.
請求項 2の保護皮膜形成方法は、 貫通孔を穿設した金属基板と、 前記貫通孔を 閉塞するように前記基板上に積層された金属箔とからなる電池用安全弁素子の、 前記金属箔の前記貫通孔を閉塞している部分の電池容器の外側となる片面に、 有 機樹脂層を設けることを特徴とする。  The method for forming a protective film according to claim 2, wherein the metal foil having a through-hole formed therein, and a metal foil laminated on the substrate so as to close the through-hole are provided. An organic resin layer is provided on one side of the portion where the through hole is closed, which is outside the battery container.
請求項 3の保護皮膜形成方法は、 貫通孔を穿設した金属基板と、 前記貫通孔を 閉塞するように前記基板上に積層された金属箔とからなる電池用安全弁素子を、 安全弁の弁口となる貫通孔を穿設した電池外装缶用の封口板に、 前記電池用安全 弁素子の金属基板の貫通孔と前記封口板の貫通孔が連通するように当接し、 前記 封口板の貫通孔の周囲で両者が接着するように接着手段を用いて接着した後、 前 記電池用安全弁素子の電池容器の外側となる片面上に有機樹脂層を設けることを 特徴とする。  The protective film forming method according to claim 3, further comprising: a battery safety valve element including a metal substrate having a through-hole formed therein, and a metal foil laminated on the substrate so as to close the through-hole. And a through-hole of the metal plate of the battery safety valve element and a through-hole of the sealing plate are in contact with a sealing plate for a battery outer can having a through-hole formed therein. After bonding using a bonding means so that the two are bonded to each other, an organic resin layer is provided on one side of the battery safety valve element that is outside the battery container.
請求項 4の保護皮膜形成方法は、 貫通孔を穿設した金属基板と、 前記貫通孔を 閉塞するように前記基板上に積層された金属箔とからなる電池用安全弁素子を、 安全弁の弁口となる貫通孔を穿設した電池外装缶用の封口板に、 前記電池用安全 弁素子の金属基板の貫通孔と前記封口板の貫通孔が連通するように当接し、 前記 封口板の貫通孔の周囲で両者が接着するように接着手段を用いて接着した後、 前 ir 記電池用安全弁素子の、 前記金属箔の前記貫通孔を閉塞している部分の電池容器 の外側となる片面上に有機樹脂層を設けることを特徴とする。 A method of forming a protective film according to claim 4, wherein the metal substrate having a through-hole is formed by: A battery safety valve element made of a metal foil laminated on the substrate so as to be closed, a battery safety canister sealing plate having a through hole formed as a valve opening of the safety valve, and a battery safety valve element of the battery safety valve element. The through-hole of the metal substrate and the through-hole of the sealing plate are in contact with each other so as to communicate with each other, and the two are adhered to each other around the through-hole of the sealing plate using bonding means. An organic resin layer is provided on one side of the element, which is the outside of the battery container, at a portion where the through hole of the metal foil is closed.
請求項 5の保護皮膜形成方法は、 前記接着手段がレーザービーム溶接であるこ とを特徴とする。  The method of forming a protective film according to claim 5, wherein the bonding means is laser beam welding.
請求項 6の保護皮膜形成方法は、 前記安全弁素子の電池容器の外側となる片面 j O 上に有機樹脂の粒を載せ、 加熱手段を用いて溶解し、 前記安全弁素子全面上に流 動させた後、 冷却手段を用いて冷却固化することにより、 前記有機樹脂層を設け ることを特徴とする。  In the method of forming a protective film according to claim 6, organic resin particles are placed on one surface j O of the safety valve element outside the battery container, melted using a heating means, and flowed over the entire surface of the safety valve element. Thereafter, the organic resin layer is provided by cooling and solidifying using a cooling means.
請求項 7の保護皮膜形成方法は、 前記安全弁素子の、 前記金属箔の前記貫通孔 を閉塞している部分の電池容器の外側となる片面上に有機樹脂の粒を載せ、 加熱 t 手段を用いて溶解し、 前記安全弁素子全面上に流動させた後、 冷却手段を用いて 冷却固化することにより、 前記有機樹脂層を設けることを特徴とする。  The method for forming a protective film according to claim 7, wherein the safety valve element is provided with a particle of an organic resin on one side of a portion of the metal foil that closes the through-hole of the metal foil on the outside of the battery container, and using a heating means. The organic resin layer is provided by dissolving and flowing over the entire surface of the safety valve element and then cooling and solidifying using a cooling means.
請求項 8の保護皮膜形成方法は、 前記有機樹脂の粒がポリプロピレン粒または ポリエチレン粒であることを特徴とする。  The protective film forming method according to claim 8, wherein the organic resin particles are polypropylene particles or polyethylene particles.
請求項 9の保護皮膜形成方法は、 前記有機樹脂の粒がパラフィンワックス粒で ； J あることを特徴とする。  A method for forming a protective film according to claim 9, wherein the organic resin particles are paraffin wax particles.
請求項 1 0の電池用安全弁素子は、 貫通孔を穿設した金属基板と、 前記貫通孔 を閉塞するように前記基板上に積層された金属箔とからなる電池用安全弁素子の 電池容器の外側となる片面に、 保護皮膜を被覆してなることを特徴とする。 請求項 1 1の電池用安全弁素子は、 貫通孔を穿設した金属基板と、 前記貫通孔 ^ を閉塞するように前記基板上に積層された金属箔とからなる電池用安全弁素子の 前記金属箔の前記貫通孔を閉塞している部分の電池容器の外側となる片面に、 保護皮膜を被覆してなることを特徴とする。 10. The battery safety valve element according to claim 10, wherein the battery safety valve element comprises a metal substrate having a through hole formed therein, and a metal foil laminated on the substrate so as to close the through hole. And a protective film is coated on one side. 12. The battery safety valve element according to claim 11, wherein the metal foil is a battery safety valve element including a metal substrate having a through hole formed therein, and a metal foil laminated on the substrate so as to close the through hole ^. On one side of the battery container outside the portion closing the through hole, It is characterized by being coated with a protective film.
請求項 1 2の電池用安全弁素子は、 前記保護皮膜が、 前記安全弁素子の電池容 器の外側となる片面上に有機樹脂の粒を載せ、 加熱手段を用いて溶解し、 前記安 全弁素子全面上に流動させた後、 冷却手段を用いて冷却固化することにより設け た有機樹脂層であることを特徴とする。  13. The safety valve element for a battery according to claim 12, wherein the protective film is formed by placing particles of an organic resin on one surface of the safety valve element that is outside a battery container, and dissolving the particles using a heating unit. It is an organic resin layer provided by flowing over the entire surface and then cooling and solidifying using cooling means.
請求項 1 3の電池用安全弁素子は、 前記保護皮膜が、 前記安全弁素子の前記金 属箔の前記貫通孔を閉塞している部分の電池容器の外側となる片面上に有機樹脂 の粒を載せ、 加熱手段を用いて溶解し、 前記安全弁素子全面上に流動させた後、 冷却手段を用いて冷却固化することにより設けた有機樹脂層であることを特徴と 13. The battery safety valve element according to claim 13, wherein the protective film has organic resin particles placed on one side of the metal foil of the safety valve element that is outside the battery container in a portion that closes the through hole. An organic resin layer provided by melting using a heating means, flowing over the entire surface of the safety valve element, and then cooling and solidifying using a cooling means.
W する。 W
請求項 1 4の電池用安全弁素子の保護皮膜形成方法は、 前記有機樹脂の粒がポ リプロピレン粒またはポリエチレン粒であることを特徴とする。  A method of forming a protective film for a safety valve element for a battery according to claim 14 is characterized in that the organic resin particles are polypropylene particles or polyethylene particles.
請求項 1 5の保護皮膜形成方法は、 前記有機樹脂の粒がパラフィンワックス粒 であることを特徴とする。  A protective film forming method according to claim 15, wherein the organic resin particles are paraffin wax particles.
請求項 1 6の電池用封口板は、 請求項 1 0〜 1 5のいずれかに記載の電池用安 全弁素子を、 安全弁の弁口となる貫通孔を穿設した電池外装缶用の封口板に、 前 記電池用安全弁素子の金属基板の貫通孔と前記封口板の貫通孔が連通するように 当接し、 前記封口板の貫通孔の周囲で両者が接着するように接着手段を用いて接 着してなることを特徴とする。 A battery sealing plate according to claim 16 is a battery sealing valve for a battery outer can, in which a battery safety valve element according to any one of claims 10 to 15 is provided with a through hole serving as a valve opening of a safety valve. The plate is brought into contact with the through hole of the metal substrate of the battery safety valve element and the through hole of the sealing plate so as to communicate with each other, and the bonding means is used so that the two are bonded around the through hole of the sealing plate. It is characterized by being attached.
0 請求項 1 7の電池用封口板は、 貫通孔を穿設した金属基板と、 前記貫通孔を閉 塞するように前記基板上に積層された金属箔とからなる電池用安全弁素子を、 安 全弁の弁口となる貫通孔を穿設した電池外装缶用の封口板に、 前記電池用安全弁 素子の金属基板の貫通孔と前記封口板の貫通孔が相対するように当接し、 前記封 口板の貫通孔の周囲で両者が接着するように接着手段を用いて接着した後、 電池 |)- 用安全弁素子の電池容器の外側となる片面上に保護皮膜を形成させてなることを 特徴とする。 請求項 1 8の電池用封口板は、 請求項 6〜 9のいずれかに記載の保護皮膜形成 方法を用いて、 前記保護皮膜を形成させてなることを特徴とする。 0 The battery sealing plate according to claim 17, further comprising: a battery safety valve element including a metal substrate having a through-hole formed therein, and a metal foil laminated on the substrate so as to close the through-hole. A sealing plate for a battery outer can having a through hole serving as a valve port of all valves is abutted so that the through hole of the metal substrate of the battery safety valve element and the through hole of the sealing plate face each other, and the sealing is performed. After bonding using a bonding means so that the two are bonded around the through hole of the mouth plate, a protective film is formed on one side of the battery container of the battery | ) -safety valve element. And A battery sealing plate according to claim 18 is characterized in that the protective film is formed using the protective film forming method according to any one of claims 6 to 9.
請求項 1 9の電池用封口板は、 前記接着手段がレーザービーム溶接であること を特徴とする。  The battery sealing plate according to claim 19, wherein the bonding means is laser beam welding.
請求項 2 0の密閉型電池は、 正極、 負極、 およびセパレー夕とで構成された電 極体が、 電解液とともに電池外装缶内に収納され、 前記電池外装缶の開口部の内 周に、 請求項 1 6〜1 9のいずれかに記載の電池用封口板を嵌入支持するように して前記電池外装缶の開口部を閉塞してなる。  In the sealed battery according to claim 20, an electrode body composed of a positive electrode, a negative electrode, and a separator is accommodated in a battery outer can together with an electrolyte, and an inner periphery of an opening of the battery outer can is provided. An opening of the battery outer can is closed by inserting and supporting the battery sealing plate according to any one of claims 16 to 19.
| 0 図面の簡単な説明 | 0 Brief Description of the Drawings
図 1は、 本発明の保護皮膜を被覆した電池用安全弁素子の一例を示す概略断面 図である。 図 2は、 本発明の保護皮膜を被覆した電池用安全弁素子の他の一例を 示す概略断面図である。 図 3は、 本発明の保護皮膜を被覆した電池用安全弁素子 の他の一例を示す概略断面図である。 図 4は、 本発明の電池用安全弁素子を接着 FIG. 1 is a schematic sectional view showing an example of a battery safety valve element coated with a protective film of the present invention. FIG. 2 is a schematic sectional view showing another example of the battery safety valve element coated with the protective film of the present invention. FIG. 3 is a schematic sectional view showing another example of the battery safety valve element coated with the protective film of the present invention. Figure 4 shows the bonding of the battery safety valve element of the present invention.
^ した電池用封口板の一例を示す概略断面図である。 図 5は、 本発明の電池用安全 弁素子を接着した電池用封口板の他の一例を示す概略断面図である。 図 6は、 本 発明の電池用安全弁素子を接着した電池用封口板の他の一例を示す概略断面図で ある。 図 7の （a ) は、 保護皮膜を被覆する前の電池用安全弁素子を接着した電 池用封口板の一例を示す概略断面図であり、 図 7の （b ) は、 本発明の保護皮膜 μ を被覆した後の電池用安全弁素子を接着した電池用封口板の一例を示す概略断面 図である。 図 8は、 本発明の電池用安全弁素子を接着した電池用封口板の他の一 例を示す概略断面図である。 FIG. 3 is a schematic cross-sectional view showing an example of a sealed battery plate. FIG. 5 is a schematic cross-sectional view showing another example of the battery sealing plate to which the battery safety valve element of the present invention is adhered. FIG. 6 is a schematic sectional view showing another example of the battery sealing plate to which the battery safety valve element of the present invention is adhered. FIG. 7 (a) is a schematic cross-sectional view showing an example of a battery sealing plate to which a safety valve element for a battery is adhered before coating with a protective film, and FIG. 7 (b) is a schematic sectional view of the protective film of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of a battery sealing plate to which a battery safety valve element after coating with μ is bonded. FIG. 8 is a schematic sectional view showing another example of the battery sealing plate to which the battery safety valve element of the present invention is adhered.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
^ 以下、 本発明の保護皮膜を被覆した電池用安全弁、 および電池用安全弁の保護 皮膜形成方法の実施例を、 図面を参照しながら説明する。 実施例 Hereinafter, embodiments of a battery safety valve coated with a protective film and a method of forming a protective film of the battery safety valve according to the present invention will be described with reference to the drawings. Example
(実施例 1 )  (Example 1)
図 1および図 2は、 本発明の保護皮膜を被覆した電池用安全弁素子の一例を示 す断面図である。 両図において、 図面上方が電池容器の外側となる側を示す。 図 IT 1に示す場合は、 本発明の安全弁素子 1 0は、 安全弁の弁口となる貫通孔 4を有 する金属基板 1の電池容器の外側となる片面に、 貫通孔 4を閉塞するように金属 箔 2が積層された積層体 5の上の、 金属箔 2の上に保護皮膜 3が形成されている 。 図 2に示す場合は、 安全弁素子 1 0は、 安全弁の弁口となる貫通孔 4を有する 金属基板 1の電池容器の内側となる側の片面に、 貫通孔 4を閉塞するように金属 , 0 箔 2が積層された積層体 5の、 金属基板 1の電池容器の外側となる片面上、 およ び金属基板 1に穿設した貫通孔 4の側壁部、 ならびに金属箔 2の貫通孔 4を閉塞 している部分に保護皮膜 3が形成されている。 すなわち、 保護皮膜 3は、 金属基 板 1に設けた貫通孔 4と金属箔 2とで形成される窪みの周囲全体を被覆し、 しか も金属基板 1上に被覆された保護皮膜 3と連続している。  1 and 2 are cross-sectional views showing one example of a battery safety valve element coated with the protective film of the present invention. In both figures, the upper side of the drawing indicates the side outside the battery container. In the case shown in FIG. IT1, the safety valve element 10 of the present invention is arranged such that the metal substrate 1 having the through hole 4 serving as the valve opening of the safety valve closes the through hole 4 on one side outside the battery container. The protective film 3 is formed on the metal foil 2 on the laminate 5 on which the metal foil 2 is laminated. In the case shown in FIG. 2, the safety valve element 10 has a through hole 4 serving as a valve opening of the safety valve. The laminated body 5 on which the foils 2 are laminated is formed on one side of the metal substrate 1 outside the battery container, the side wall of the through hole 4 formed in the metal substrate 1, and the through hole 4 of the metal foil 2. The protective film 3 is formed on the closed part. That is, the protective film 3 covers the entire periphery of the depression formed by the through hole 4 provided in the metal substrate 1 and the metal foil 2, and is continuous with the protective film 3 coated on the metal substrate 1. ing.
jt 図 3は、 本発明の保護皮膜を被覆した電池用安全弁素子の他の例を示す断面図 である。 図 3に示すように、 本発明の安全弁素子 1 0は、 安全弁の弁口となる貫 通孔 4を有する金属基板 1の電池容器の内側となる側の片面に、 貫通孔 4を閉塞 するように金属箔 2が積層された積層体 5において、 金属箔 2の貫通孔 4を閉塞 している部分 4 aのみに、 保護皮膜 3を形成されている。 jt FIG. 3 is a cross-sectional view showing another example of the battery safety valve element coated with the protective film of the present invention. As shown in FIG. 3, the safety valve element 10 of the present invention closes the through hole 4 on one side of the metal substrate 1 having the through hole 4 serving as the valve opening of the safety valve on the side inside the battery container. In the laminate 5 in which the metal foil 2 is laminated on the metal foil 2, the protective film 3 is formed only on the portion 4 a of the metal foil 2 that closes the through hole 4.
^ 本発明の対象とする個々の電池用安全弁素子 1 0は次のようにして作成される 。 まず、 弁口となる貫通孔 4を複数個穿孔した長尺帯状の金属基板 1の片面に、 前記貫通孔 4を閉塞するように金属箔 2を積層して、 長尺帯状の積層体 5を作成 する。 貫通孔 4は通常は直径 1〜 1 0 mmの円が用いられるが、 長径が 1〜 1 0 mmの楕円、 もしくは上記円の直怪に相当する大きさの多角形であってもよい。 ^ The individual safety valve element 10 for a battery according to the present invention is prepared as follows. First, a metal foil 2 is laminated on one surface of a long strip-shaped metal substrate 1 in which a plurality of through holes 4 serving as valve ports are perforated so as to close the through holes 4, and a long strip-shaped laminate 5 is formed. create. The through-hole 4 is usually a circle having a diameter of 1 to 10 mm, but may be an ellipse having a major axis of 1 to 10 mm, or a polygon having a size corresponding to the direct shape of the circle.
^ また貫通孔 4の形状は、 一定幅を有する線分 （例えば、 直線や曲線からなるスリ ット） や、 上記の図形を組み合わせた幾何学模様の貫通孔であってもよい。 貫通 孔 4の配列は、 格子状配列、 千鳥状配列などの幾何学的に配列されていることが 好ましく、 貫通孔 4同士のピッチは必要とされる安全弁用部材の大きさによって 適宜選択される。 貫通孔 4は、 冷間圧延で薄板にしたものを打ち抜きプレスゃェ ツチングなどの通常の穿孔法を用いて形成することができる。 ^ Further, the shape of the through hole 4 may be a line segment having a constant width (for example, a slit formed of a straight line or a curve) or a through hole having a geometric pattern obtained by combining the above figures. Penetrating The arrangement of the holes 4 is preferably a geometric arrangement such as a lattice arrangement or a staggered arrangement, and the pitch between the through holes 4 is appropriately selected according to the required size of the safety valve member. The through-holes 4 can be formed by using a normal perforation method such as punching and punching of a thin plate formed by cold rolling.
if 上記のようにして貫通孔 4が穿設された金属基板 1と金属箔 2は、 例えば特開 平 1 一 2 2 4 1 8 4号公報に記載された方法を用いて、 真空中で冷間圧接される すなわち、 金属基板 1と金属箔 2の互いに積層される面をエッチングチヤンバー 内でスパッタリング処理して活性化した後、 真空槽内に設けた圧延ュニッ卜で冷 10 間圧接する。 このようにして、 本発明の長尺帯状の積層体 5が作成される。  if The metal substrate 1 and the metal foil 2 in which the through-holes 4 are formed as described above are cooled in a vacuum, for example, by using a method described in Japanese Patent Application Laid-Open No. 122224/1994. That is, after the surfaces of the metal substrate 1 and the metal foil 2 to be laminated are activated by sputtering in an etching chamber, they are cold pressed by a rolling unit provided in a vacuum chamber. Thus, the long strip-shaped laminate 5 of the present invention is produced.
次いで、 この長尺帯状の積層体から少なくとも 1個の穿接された貫通孔が含ま れるようにして打ち抜きパンチを用いて打ち抜くなどして、 個々の電池用安全弁 素子 1 0を多数個得ることができる。  Next, a large number of individual battery safety valve elements 10 can be obtained by punching out from the long band-shaped laminate using a punching punch so as to include at least one perforated through hole. it can.
図 1に示した実施例においては、 上記のようにして作成した個々の電池用安全 ^ 弁素子 1 0の積層体 5の金属箔 2の電池容器の外側となる面全体に有機樹脂層を 被覆して保護皮膜 3とする。  In the embodiment shown in FIG. 1, the entire surface of the metal foil 2 of the laminated body 5 of the individual battery safety valve elements 10 formed as described above and the metal foil 2 is covered with the organic resin layer. To form a protective film 3.
図 2に示した実施例においては、 電池用安全弁素子 1 0の積層体 5の金属基板 1の電池容器の外側となる面、 および金属基板 1に穿設した貫通孔 4の側壁部、 ならびに金属箔 2の貫通孔 4を閉塞している部分に有機樹脂層を被覆して保護皮μ ■ 膜 3とする。  In the embodiment shown in FIG. 2, the outer surface of the metal container 1 of the metal substrate 1 of the laminated body 5 of the battery safety valve element 10 and the side wall of the through hole 4 formed in the metal substrate 1 and the metal An organic resin layer is coated on the portion of the foil 2 that closes the through hole 4 to form a protective skin μ film 3.
図 3に示した実施例においては、 電池用安全弁素子 1 0の積層体 5の金属基板 1に穿設した貫通孔 4を閉塞している金属箔 2の部分に有機樹脂層を被覆して保 護皮膜 3とする。  In the embodiment shown in FIG. 3, an organic resin layer is applied to cover a portion of the metal foil 2 which closes the through hole 4 formed in the metal substrate 1 of the laminated body 5 of the battery safety valve element 10 and is held. Protective coating 3.
前記金属基板 1としては、 鋼板、 ステンレス鋼板、 銅板、 アルミニウム板のい ^ ずれかであることが好ましい。 板厚は強度的、 および経済的観点、 さらに電池外 装缶用の封口板への接着し易さの観点から、 通常は 0 . 0 3〜2 . 0 mmであり、 より好ましくは 0 . 0 5〜 1 . 5 mmである。 The metal substrate 1 is preferably any one of a steel plate, a stainless steel plate, a copper plate, and an aluminum plate. The plate thickness is usually from 0.03 to 2.0 mm from the viewpoints of strength and economy, and from the viewpoint of easy adhesion to the sealing plate for the battery outer can. More preferably, it is 0.05 to 1.5 mm.
本発明の電池用安全弁素子は、 3 0 k g f c m2 以下、 好ましくは 2 0 k g f / c m2 以下の低圧で作動することを目的としている。 そのため、 本発明に用 いる金属箔の厚さとしては 5〜 1 5 0 mであることが好ましい。 5 /x m未満で If あると、 電池などの安全弁に適用した場合、 落下などの衝撃で容易に破断してし まう。 一方 1 5 0 x mを超えると、 破断強度の小さな金属を用いても、 安全弁に 適用した場合、 3 0 k g f / c m2 以下の圧力では破断せず、 高圧が負荷されて 初めて破断するため、 電池ケース自体が破裂し、 破片が飛散したり、 電解液が吹 き出して飛散したりして、 安全性が損なわれる。 また、 コスト的に不利になる。 (0 ゆえに、 前記金属箔 2としては、 鋼箔、 ステンレス鋼箔、 銅箔、 アルミニウム箔 、 ニッケル箔、 ニッケル—鉄合金箔のいずれかであることが好ましい。 さらに、 電池ケース内に充填される電解液に対して安定であり、 腐食したり反応ガスなど が多量に発生しない限り、 如何なる金属箔を用いても差し支えなく、 上記の箔の 他に、 亜鉛、 鉛、 真鍮、 青銅、 リン青銅、 砲金、 モネルなどの銅合金、 ジュラルlf ミンなどのアルミニウム合金などからなる金属箔も適用可能である。 The battery safety valve element of the present invention is intended to operate at a low pressure of 30 kgfcm 2 or less, preferably 20 kgf / cm 2 or less. Therefore, the thickness of the metal foil used in the present invention is preferably 5 to 150 m. If it is less than 5 / xm, if it is applied to a safety valve such as a battery, it will be easily broken by impact such as dropping. If the amount exceeds 1 5 0 xm, even using a small metal breaking strength, when applied to the safety valve, 3 0 kgf / cm 2 without fracture at pressures, for the first time breaking it is high load, battery The case itself ruptures, shards are scattered, and the electrolyte blows out and splatters, impairing safety. It is also disadvantageous in terms of cost. (Therefore, it is preferable that the metal foil 2 is any one of a steel foil, a stainless steel foil, a copper foil, an aluminum foil, a nickel foil, and a nickel-iron alloy foil. Any metal foil can be used as long as it is stable against the electrolyte and does not corrode or generate a large amount of reaction gas.In addition to the above foils, zinc, lead, brass, bronze, phosphor bronze, Metal foils made of copper alloys such as gunmetal and monel, and aluminum alloys such as duralfmin are also applicable.
次に、 本発明においては、 上記の図 1から 3に示した電池用安全弁素子の保護 皮膜 3の有機樹脂層は、 金属基板 1または金属箔 2の有機樹脂層で被覆する部分 に有機樹脂の粒を載せ、 加熱手段を用いて溶解し、 被覆する面上全体に流動させ た後、 冷却手段を用いて冷却固化することにより形成させる。 加熱および冷却手 段としては、 それぞれ熱風ヒーターや冷風クーラ一による送風、 加熱したブロッ クおよび冷却したブロックに載せることによるブロックからの熱伝導などの方法 を用いることができる。  Next, in the present invention, the organic resin layer of the protective film 3 of the safety valve element for a battery shown in FIGS. 1 to 3 above is formed by coating the organic resin layer on the portion covered with the organic resin layer of the metal substrate 1 or the metal foil 2. The particles are placed, melted using a heating means, allowed to flow over the entire surface to be coated, and then cooled and solidified using a cooling means to form the particles. As the heating and cooling means, there can be used, for example, a method of blowing air by a hot air heater or a cool air cooler, and a method of conducting heat from a block by placing it on a heated block or a cooled block.
被覆する有機樹脂の種類としては、 ポリオレフイン樹脂、 ポリエステル樹脂、 ポリアミド樹脂、 ボリカーボネート樹脂、 ポリ塩化ビニル樹脂 ポリウレ夕ン樹 脂、 パラフィンワックス、 マイクロクリスタリンワックス、 ペトロレイタム、 木 ロウ、 マレイン酸で変性したポリオレフイン樹脂、 未変性のポリオレフイン樹脂 が適用できる。 また、 有機樹脂としては粒径が 0 . l〜2 mm程度の粒状の樹脂 を用い、 被覆する部分の面積に応じてその部分に載せる粒子の数を調節する。 有 機樹脂としては加熱溶解した際に粘度が低く流動性に富む性質を有しているもの が好ましく、 融点が 6 0〜2 0 0 °Cであるポリオレフイン樹脂、 ポリエステル樹Types of organic resin to be coated include polyolefin resin, polyester resin, polyamide resin, polycarbonate resin, polyvinyl chloride resin, polyurethane resin, paraffin wax, microcrystalline wax, petroleum, wood wax, and polyolefin modified with maleic acid. Resin, unmodified polyolefin resin Can be applied. In addition, as the organic resin, a granular resin having a particle size of about 0.1 to 2 mm is used, and the number of particles to be placed on the portion to be covered is adjusted according to the area of the portion to be covered. As the organic resin, those having a low viscosity and high fluidity when melted by heating are preferable.Polyolefin resins and polyester resins having a melting point of 60 to 200 ° C.
/Γ 脂、 ポリアミド樹脂、 ポリカーボネート樹脂、 ポリ塩化ビニル樹脂 ポリウレタ ン樹脂などの熱可塑性樹脂や、 パラフィンワックス、 マイクロクリス夕リンヮッ クス、 ペトロレイタム、 木ロウなどのワックスが適用可能であるが、 熱可塑性樹 脂としては、 金属との接着性を向上させるためにマレイン酸で変性したポリオレ フィン樹脂はもとより、 金属との接着性を有していない通常の未変性のポリオレ / Thermoplastic resins such as resin, polyamide resin, polycarbonate resin, polyvinyl chloride resin, and urethane resin, and waxes such as paraffin wax, microcrystalline silica, petroleum, and wood wax are applicable. As fats and oils, not only polyolefin resins modified with maleic acid to improve adhesion to metals, but also ordinary unmodified polyolefins that do not have adhesion to metals
[ 0 フィン樹脂も好適に使用可能である。 ワックスとしてはパラフィンワックスを用 いることが好ましい。  [0] Fin resins can also be suitably used. It is preferable to use paraffin wax as the wax.
これらの有機樹脂粒を加熱溶融し、 冷却固化させた後も有機樹脂層の厚さは 2 〜5 0 i mであることが好ましく、 より好ましくは 1 0〜3 0 z mである。 2 w m未満であると、 有機樹脂層で金属基板や板金属箔を完全に被覆することが困難 Even after these organic resin particles are heated and melted and solidified by cooling, the thickness of the organic resin layer is preferably 2 to 50 im, more preferably 10 to 30 zm. If it is less than 2 wm, it is difficult to completely cover the metal substrate or sheet metal foil with the organic resin layer
( If であり、 樹脂フィルムの場合はフィルムとして製膜することが極めて困難となる 。 一方 5 を超えると、 金属箔が所定の負荷圧力で破断せず、 所定の破断圧 力を上回る負荷圧力が作用して初めて破断するようになり、 安全弁としての機能 が損なわれる。 また、 コスト的にも有利でなくなる。 (If, in the case of resin film, it is extremely difficult to form a film as a film. On the other hand, if it exceeds 5, the metal foil will not break at the predetermined load pressure, and the load pressure exceeding the predetermined break pressure will increase. It breaks only when it is actuated, impairing its function as a safety valve, and is not advantageous in terms of cost.
(実施例 2 )  (Example 2)
^ 上記のようにして作成された本発明の安全弁素子 1 0は、 図 4〜6に示すよう に、 安全弁の弁口となる貫通孔 7を穿設した電池外装缶用の封口板 6に、 安全弁 素子 1 0の金属基板 1の貫通孔 4と電池外装缶用の封口板 6の貫通孔 7が連通す るように当接し、 貫通孔 7の周囲をレーザービーム溶接法などの接着手段を用い て接着する。 図 4は図 1に示した構造を有する安全弁素子を電池外装缶用の封口 板に接着した場合を示す。 図 5および図 6は、 それぞれ図 2および図 3に示した 構造を有する安全弁素子を電池外装缶用の封口板に接着した場合を示す。 接着手段としては前記レーザ一ビーム溶接法に限定するものではなく、 熱硬化 性樹脂系の接着剤や熱可塑性樹脂系接着剤、 ゴム系接着剤などの接着剤を用いる 接着法など、 必要な接着強度が得られる限り、 如何なる接着手段を用いてもよい 図 4〜 6においては電池外装缶用の封口板 6の貫通孔 7の 1個に安全弁素子 1 0の金属基板 1の貫通孔 4の 1個が連通するように当接して接着した場合を示し たが、 電池外装缶用の封口板 6の貫通孔 7の 1個に安全弁素子 1 0の金属基板 1 の貫通孔 4が複数個連通するように当接して接着してもよい。 前記封口板として は、 前記金属基板と同様に、 鋼板、 ステンレス鋼板、 銅板、 アルミニウム板のい ずれかであることが好ましい。 板厚は強度的、 および経済的観点、 さらに金属基 板への接着し易さの観点から、 通常は 0 . 0 3〜2 . O mmであり、 より好ましく は 0 . 0 5〜： L . 5 mmである。 ^ The safety valve element 10 of the present invention created as described above has a sealing plate 6 for a battery outer can having a through hole 7 as a valve port of a safety valve as shown in FIGS. The through-hole 4 of the metal substrate 1 of the safety valve element 10 is in contact with the through-hole 7 of the sealing plate 6 for the battery outer can in such a way that the through-hole 7 communicates with the through-hole 7, and an adhesive means such as laser beam welding is used around the through-hole 7. And glue. Fig. 4 shows a case where the safety valve element having the structure shown in Fig. 1 is bonded to a sealing plate for a battery outer can. FIGS. 5 and 6 show a case where the safety valve element having the structure shown in FIGS. 2 and 3, respectively, is bonded to a sealing plate for a battery outer can. The bonding means is not limited to the laser one-beam welding method, but may be a necessary bonding method such as a bonding method using an adhesive such as a thermosetting resin-based adhesive, a thermoplastic resin-based adhesive, or a rubber-based adhesive. Any bonding means may be used as long as strength can be obtained.In FIGS. 4 to 6, one of the through holes 7 in the sealing plate 6 for the battery outer can is provided with one of the through holes 4 in the metal substrate 1 of the safety valve element 10. In this case, a plurality of through holes 4 in the metal substrate 1 of the safety valve element 10 communicate with one of the through holes 7 in the sealing plate 6 for the battery outer can. May be abutted and adhered. The sealing plate is preferably any of a steel plate, a stainless steel plate, a copper plate, and an aluminum plate, like the metal substrate. The plate thickness is usually from 0.03 to 2.0 mm, more preferably from 0.05 to L: from the viewpoint of strength and economy, and further from the viewpoint of easy adhesion to the metal substrate. 5 mm.
(実施例 3 )  (Example 3)
また、 本発明の保護皮膜を被覆した電池用安全弁素子を接着した電池外装缶用 の封口板は、 図 7の （a ) および （b ) に示すようにして作成してもよい。 すな わち、 図 7の （a ) に示すように、 貫通孔 4を穿設した金属基板 1と、 貫通孔 4 を閉塞するように金属基板 1上に積層された金属箔 2とからなる電池用安全弁素 子 1 0を、 安全弁の弁口となる貫通孔 7を穿設した電池外装缶用の封口板 6に、 前記電池用安全弁素子 1 0の金属基板 1の貫通孔 4と封口板 6の貫通孔 7が連通 するように当接し、 封口板 6の貫通孔 7の周囲で両者が接着するようにレーザー ビーム法を用いて接着した後、 図 7の （b ) に示すように、 溶接部分も含めて電 池用安全弁素子 1 0上に有機樹脂層を形成させて保護皮膜 3を設けてもよい。 こ のように、 レーザ一ビーム溶接後に、 溶接部分も含めて電池用安全弁素子上に保 護皮膜を設けることにより、 貫通孔部を閉塞する金属箔、 および金属部分が露出 するレーザービーム溶接部が保護皮膜で被覆されるので、 腐食性の強い電解液が 付着しても金属部分が腐食して穿孔することがない。 (実施例 4 ) Further, a sealing plate for a battery outer can to which a battery safety valve element coated with a protective film of the present invention is adhered may be prepared as shown in FIGS. 7 (a) and (b). That is, as shown in FIG. 7 (a), a metal substrate 1 having a through-hole 4 and a metal foil 2 laminated on the metal substrate 1 so as to close the through-hole 4 are formed. The battery safety valve element 10 is inserted into a sealing plate 6 for a battery outer can having a through hole 7 serving as a valve opening of the safety valve, and the through hole 4 of the metal substrate 1 of the battery safety valve element 10 and the sealing plate. The through holes 7 of 6 are connected so as to communicate with each other, and the two are adhered to each other around the through hole 7 of the sealing plate 6 by using a laser beam method, and then, as shown in (b) of FIG. The protective film 3 may be provided by forming an organic resin layer on the battery safety valve element 10 including the welded portion. In this way, after the laser one-beam welding, by providing a protective film on the battery safety valve element including the welded part, the metal foil that closes the through hole and the laser beam weld that exposes the metal part are formed. Since it is covered with a protective film, even if a highly corrosive electrolytic solution adheres, the metal parts do not corrode and do not pierce. (Example 4)
図 4〜 7は封口板 6の貫通孔 7の径と同一径の外径を有する安全弁素子 1 0を 、 封口板 6の貫通孔 7に嵌入して接着することにより、 安全弁素子 1 0の金属基 板 1の貫通孔 4と封口板 6の貫通孔 7を連通させる構造としているが、 図 8に示 すように、 封口板 6の貫通孔 7の径より大径の外径を有する安全弁素子 1 0を、 安全弁素子 1 0の金属基板 1の貫通孔 4と封口板 6の貫通孔 7が連通するように 、 封口板 6に重ね合わせて当接して接着してもよい。  FIGS. 4 to 7 show that the safety valve element 10 having the same outer diameter as the diameter of the through-hole 7 of the sealing plate 6 is fitted into and adhered to the through-hole 7 of the sealing plate 6, thereby forming a metal for the safety valve element 10. The through hole 4 of the base plate 1 and the through hole 7 of the sealing plate 6 communicate with each other.As shown in Fig. 8, the safety valve element has an outer diameter larger than the diameter of the through hole 7 of the sealing plate 6. 10 may be superimposed on and contacted with the sealing plate 6 so that the through hole 4 of the metal substrate 1 of the safety valve element 10 and the through hole 7 of the sealing plate 6 communicate with each other.
以上のようにして本発明の保護皮膜を被覆した電池用安全弁素子を装着した電 池外装缶用の封口板を、 正極、 負極、 およびセパレー夕とで構成された電極体が 電解液とともに収納された電池外装缶の開口部の内周に嵌入支持するようにして 前記電池外装缶の開口部を閉塞することにより、 本発明の密閉型電池が得られる 産業上の利用可能性  As described above, a sealing plate for a battery outer can equipped with a battery safety valve element coated with a protective film of the present invention is stored in an electrode body including a positive electrode, a negative electrode, and a separator together with an electrolyte. The sealed battery of the present invention can be obtained by closing the opening of the battery outer can so as to fit and support the inner periphery of the opening of the battery outer can.
本発明は、 貫通孔を穿設した金属基板と、 前記貫通孔を閉塞するように前記基 板上に積層された金属箔とからなる電池用安全弁素子の電池容器の外側となる片 面に、 有機樹脂層を設けることを特徴とする、 電池用安全弁素子の保護皮膜形成 方法、 これらの保護皮膜形成方法を用いて作成した電池用安全弁素子の保護皮膜 である。 また本発明は、 前記の電池用安全弁素子を、 安全弁の弁口となる貫通孔 を穿設した電池外装缶用の封口板に、 電池用安全弁素子の金属基板の貫通孔と封 口板の貫通孔が相対するように当接し、 前記封口板の貫通孔の周囲で両者が接着 するように接着手段を用いて接着してなる電池用封口板、 およびその電池用封口 板を用いて、 正極、 負極、 およびセパレー夕とで構成された電極体が電解液とと もに収納された電池外装缶の開口部の内周に嵌入支持するようにして前記電池外 装缶の開口部を閉塞してなる密閉型電池である。 本発明の封口板を用いた密閉型 電池においては、 支持電解質としてリチウムのフッ素化合物を含み、 電池容器内 部においては電池容器や安全弁素子を構成する金属材料を腐食することはないが 、 大気中においてはフッ素化合物が大気中の水分を吸収してフッ化水素酸となる ために強い腐食性を有する非水電解液が飛散し、 電池容器の外部、 特に安全弁素 子の金属箔に付着しても、 金属箔上に保護皮膜が存在するために、 薄い金属箔が 腐食により穿孔することがない。 The present invention relates to a battery safety valve element comprising a metal substrate having a through-hole formed therein and a metal foil laminated on the substrate so as to close the through-hole, on one side which is outside the battery container. A method for forming a protective film for a battery safety valve element, comprising providing an organic resin layer, and a protective film for a battery safety valve element prepared using these methods. Further, the present invention provides a battery safety valve element as described above, wherein a battery safety canister is provided with a through-hole formed in a metal substrate of a battery safety canister and a through-hole of the sealing plate. The battery sealing plate is abutted so that the holes are opposed to each other, and is bonded by using an adhesive means so that the two are bonded around the through hole of the sealing plate, and a positive electrode, The opening of the battery outer can is closed by inserting and supporting the electrode body composed of the negative electrode and the separator into the inner periphery of the opening of the battery outer can housed together with the electrolytic solution. Sealed battery. The sealed battery using the sealing plate of the present invention contains a fluorine compound of lithium as a supporting electrolyte, and does not corrode the metal material constituting the battery container and the safety valve element inside the battery container. However, in the atmosphere, the fluorine compound absorbs moisture in the atmosphere to form hydrofluoric acid, and the highly corrosive non-aqueous electrolyte scatters, causing the non-aqueous electrolyte to scatter outside the battery container, especially on the metal foil of the safety valve element Even if it adheres, the thin metal foil does not pierce due to corrosion due to the presence of the protective film on the metal foil.

Claims

請 求 の 範 囲 The scope of the claims
1 . 貫通孔を穿設した金属基板と、 前記貫通孔を閉塞するように前記基板上に 積層された金属箔とからなる電池用安全弁素子の電池容器の外側となる片面に、1. On one side of a battery safety valve element comprising a metal substrate having a through hole and a metal foil laminated on the substrate so as to close the through hole, which is outside the battery container.
I 有機樹脂層を設けることを特徴とする、 電池用安全弁素子の保護皮膜形成方法。 I A method for forming a protective film for a safety valve element for a battery, comprising providing an organic resin layer.
2 . 貫通孔を穿設した金属基板と、 前記貫通孔を閉塞するように前記基板上に 積層された金属箔とからなる電池用安全弁素子の、 前記金属箔の前記貫通孔を閉 塞している部分の電池容器の外側となる片面に、 有機樹脂層を設けることを特徴 とする、 電池用安全弁素子の保護皮膜形成方法。  2. A battery safety valve element including a metal substrate having a through hole and a metal foil laminated on the substrate so as to close the through hole, wherein the through hole of the metal foil is closed. A method for forming a protective film for a safety valve element for a battery, comprising: providing an organic resin layer on one side of a portion of the battery container outside the battery container.
| 0 3 . 貫通孔を穿設した金属基板と、 前記貫通孔を閉塞するように前記基板上に 積層された金属箔とからなる電池用安全弁素子を、 安全弁の弁口となる貫通孔を 穿設した電池外装缶用の封口板に、 前記電池用安全弁素子の金属基板の貫通孔と 前記封口板の貫通孔が連通するように当接し、 前記封口板の貫通孔の周囲で両者 が接着するように接着手段を用いて接着した後、 前記電池用安全弁素子の電池容 itr 器の外側となる片面上に有機樹脂層を設けることを特徴とする、 電池用安全弁素 子の保護皮膜形成方法。  | 0 3. A battery safety valve element including a metal substrate having a through hole and a metal foil laminated on the substrate so as to close the through hole is provided with a through hole serving as a valve opening of the safety valve. The through-hole of the metal substrate of the battery safety valve element and the through-hole of the sealing plate are in contact with the provided sealing plate for the battery outer can, and both are bonded around the through-hole of the sealing plate. A method for forming a protective film for a battery safety valve element, comprising: providing an organic resin layer on one side of the battery safety valve element outside the battery container after the bonding using the bonding means.
4 . 貫通孔を穿設した金属基板と、 前記貫通孔を閉塞するように前記基板上に 積層された金属箔とからなる電池用安全弁素子を、 安全弁の弁口となる貫通孔を 穿設した電池外装缶用の封口板に、 前記電池用安全弁素子の金属基板の貫通孔と ' ) 前記封口板の貫通孔が連通するように当接し、 前記封口板の貫通孔の周囲で両者 が接着するように接着手段を用いて接着した後、 前記電池用安全弁素子の、 前記 金属箔の前記貫通孔を閉塞している部分の電池容器の外側となる片面上に有機樹 脂層を設けることを特徴とする、 電池用安全弁素子の保護皮膜形成方法。  4. A battery safety valve element composed of a metal substrate having a through hole and a metal foil laminated on the substrate so as to close the through hole is provided with a through hole serving as a valve port of the safety valve. A) contact the through hole of the metal substrate of the battery safety valve element with the sealing plate for the battery outer can so that the through hole of the sealing plate communicates with each other, and adhere to the periphery of the through hole of the sealing plate. After bonding using a bonding means as described above, an organic resin layer is provided on one side of the battery safety valve element, which is a portion of the metal foil that closes the through hole and is outside the battery container. A method for forming a protective film on a safety valve element for a battery.
5 . 前記接着手段がレーザービーム溶接であることを特徴とする、 請求項 3又 ^ は 4に記載の電池用安全弁素子の保護皮膜形成方法。  5. The method for forming a protective film on a safety valve element for a battery according to claim 3 or 4, wherein the bonding means is laser beam welding.
6 . 前記安全弁素子の電池容器の外側となる片面上に有機樹脂の粒を載せ、 加 熱手段を用いて溶解し、 前記安全弁素子全面上に流動させた後、 冷却手段を用い て冷却固化することにより、 前記有機樹脂層を設けることを特徴とする、 請求項 1又は 3に記載の電池用安全弁素子の保護皮膜形成方法。 6. Place the organic resin particles on one side of the safety valve element outside the battery container, The method according to claim 1, wherein the organic resin layer is provided by melting using a heating means, flowing over the entire surface of the safety valve element, and then solidifying by cooling using a cooling means. Method for forming protective film of battery safety valve element.
7 . 前記安全弁素子の、 前記金属箔の前記貫通孔を閉塞している部分の電池容 If 器の外側となる片面上に有機樹脂の粒を載せ、 加熱手段を用いて溶解し、 前記安 全弁素子全面上に流動させた後、 冷却手段を用いて冷却固化することにより、 前 記有機樹脂層を設けることを特徴とする、 請求項 2又は 4に記載の電池用安全弁 素子の保護皮膜形成方法。  7. The organic resin particles are placed on one side of the safety valve element, which is the outside of the battery case where the through hole of the metal foil is closed, and melted using a heating means, and the safety is removed. The protective film for a battery safety valve element according to claim 2 or 4, wherein the organic resin layer is provided by flowing the liquid over the entire surface of the valve element and then cooling and solidifying using a cooling means. Method.
8 . 前記有機樹脂の粒がポリプロピレン粒またはポリエチレン粒である、 請求 10 項 6又は 7に記載の電池用安全弁素子の保護皮膜形成方法。  8. The method for forming a protective film for a battery safety valve element according to claim 6, wherein the organic resin particles are polypropylene particles or polyethylene particles.
9 . 前記有機樹脂の粒がパラフィンワックス粒である、 請求項 6又は 7に記載 の電池用安全弁素子の保護皮膜形成方法。  9. The method according to claim 6 or 7, wherein the organic resin particles are paraffin wax particles.
1 0 . 貫通孔を穿設した金属基板と、 前記貫通孔を閉塞するように前記基板上 に積層された金属箔とからなる電池用安全弁素子の電池容器の外側となる片面に 10. A battery safety valve element comprising a metal substrate having a through-hole and a metal foil laminated on the substrate so as to close the through-hole is provided on one side of the battery container outside the battery container.
\ f 、 保護皮膜を被覆してなる電池用安全弁素子。 \ f, Battery safety valve element coated with a protective film.
1 1 . 貫通孔を穿設した金属基板と、 前記貫通孔を閉塞するように前記基板上 に積層された金属箔とからなる電池用安全弁素子の、 前記金属箔の前記貫通孔を 閉塞している部分の電池容器の外側となる片面に、 保護皮膜を被覆してなる電池 用安全弁素子。  1 1. A battery safety valve element including a metal substrate having a through hole and a metal foil laminated on the substrate so as to close the through hole, wherein the through hole of the metal foil is closed. A safety valve element for batteries in which a protective film is coated on one side outside the battery container.
^ 1 2 . 前記保護皮膜が、 前記安全弁素子の電池容器の外側となる片面上に有機 樹脂の粒を載せ、 加熱手段を用いて溶解し、 前記安全弁素子全面上に流動させた 後、 冷却手段を用いて冷却固化することにより設けた有機樹脂層であることを特 徴とする、 請求項 1 0に記載の電池用安全弁素子。  ^ 12. The protective film is placed on one side of the safety valve element outside the battery container, and the organic resin particles are melted by heating means, allowed to flow over the entire surface of the safety valve element, and then cooled. The safety valve element for a battery according to claim 10, characterized in that it is an organic resin layer provided by cooling and solidifying using a liquid.
1 3 . 前記保護皮膜が、 前記安全弁素子の前記金属箔の前記貫通孔を閉塞して ^J いる部分の電池容器の外側となる片面上に有機樹脂の粒を載せ、 加熱手段を用い て溶解し、 前記安全弁素子全面上に流動させた後、 冷却手段を用いて冷却固化す ることにより設けた有機樹脂層であることを特徴とする、 請求項 1 1に記載の電 池用安全弁素子。 13. The organic resin particles are placed on the outer surface of the battery container at the portion where the protective film closes the through-hole of the metal foil of the safety valve element and melted using a heating means. After flowing over the entire surface of the safety valve element, it is cooled and solidified using cooling means. 21. The battery safety valve element according to claim 11, wherein the battery safety valve element is an organic resin layer provided by forming.
1 4 . 前記有機樹脂の粒がポリプロピレン粒またはポリエチレン粒である、 請 求項 1 2または 1 3に記載の電池用安全弁素子の保護皮膜形成方法。  14. The method for forming a protective film for a battery safety valve element according to claim 12, wherein the organic resin particles are polypropylene particles or polyethylene particles.
f 1 5 . 前記有機樹脂の粒がパラフィンワックス粒である、 請求項 1 2又は 1 3 に記載の電池用安全弁素子の保護皮膜形成方法。  f 15. The method of forming a protective film for a battery safety valve element according to claim 12, wherein the organic resin particles are paraffin wax particles.
1 6 . 請求項 1 0〜 1 5のいずれかに記載の電池用安全弁素子を、 安全弁の弁 口となる貫通孔を穿設した電池外装缶用の封口板に、 前記電池用安全弁素子の金 属基板の貫通孔と前記封口板の貫通孔が連通するように当接し、 前記封口板の貫 IC 通孔の周囲で両者が接着するように接着手段を用いて接着してなる電池用封口板  16. The battery safety valve element according to any one of claims 10 to 15 is mounted on a sealing plate for a battery outer can having a through hole formed as a valve opening of the safety valve, by using the metal of the battery safety valve element. A battery sealing plate that is in contact with the through hole of the metal substrate and the through hole of the sealing plate so as to communicate with each other, and is bonded using an adhesive means such that the two are bonded around the through IC through hole of the sealing plate.
1 7 . 貫通孔を穿設した金属基板と、 前記貫通孔を閉塞するように前記基板上 に積層された金属箔とからなる電池用安全弁素子を、 安全弁の弁口となる貫通孔 を穿設した電池外装缶用の封口板に、 前記電池用安全弁素子の金属基板の貫通孔17. A battery safety valve element composed of a metal substrate having a through hole and a metal foil laminated on the substrate so as to close the through hole, and a through hole serving as a valve opening of the safety valve. Through-holes in the metal substrate of the battery safety valve element
\ tf と前記封口板の貫通孔が相対するように当接し、 前記封口板の貫通孔の周囲で両 者が接着するように接着手段を用いて接着した後、 電池用安全弁素子の電池容器 の外側となる片面上に保護皮膜を形成させてなる電池用封口板。 \ tf is abutted so that the through hole of the sealing plate faces each other, and the two are adhered to each other around the through hole of the sealing plate using bonding means. A battery sealing plate having a protective film formed on one side serving as the outside.
1 8 . 請求項 6〜 9のいずれかに記載の保護皮膜形成方法を用いて、 前記保護 皮膜を形成させてなる、 請求項 1 7に記載の電池用封口板。  18. The battery sealing plate according to claim 17, wherein the protective film is formed using the protective film forming method according to any one of claims 6 to 9.
X？ 1 9 . 前記接着手段がレーザービーム溶接であることを特徴とする、 請求項 1 6又は 1 7に記載の電池用封口板。  X? 19. The battery sealing plate according to claim 16 or 17, wherein the bonding means is laser beam welding.
2 0 . 正極、 負極、 およびセパレー夕とで構成された電極体が、 電解液ととも に電池外装缶内に収納され、 前記電池外装缶の開口部の内周に、 請求項 1 6〜 1 9のいずれかに記載の電池用封口板を嵌入支持するようにして前記電池外装缶の ^開口部を閉塞してなる密閉型電池。  20. An electrode body composed of a positive electrode, a negative electrode, and a separator is housed in a battery outer can together with an electrolytic solution, and is provided on an inner periphery of an opening of the battery outer can. 10. A sealed battery in which the opening of the battery outer can is closed so as to fit and support the battery sealing plate according to any one of 9.
PCT/JP2000/003322 1999-05-24 2000-05-24 Method for forming protective coating for cell safety valve device, cell safety valve device covered with protective coating, cell sealing plate comprising the same, and closed cell comprising the same WO2000072388A1 (en)

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