JP6913440B2 - Metal plate for battery container and method for manufacturing this metal plate for battery container - Google Patents
Metal plate for battery container and method for manufacturing this metal plate for battery container Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims description 183
- 239000002184 metal Substances 0.000 title claims description 183
- 238000000034 method Methods 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- -1 polypropylene Polymers 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 23
- 239000002335 surface treatment layer Substances 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 229920001225 polyester resin Polymers 0.000 claims description 20
- 229920005992 thermoplastic resin Polymers 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 17
- 239000004645 polyester resin Substances 0.000 claims description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 11
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 11
- 229920005672 polyolefin resin Polymers 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 8
- 238000005097 cold rolling Methods 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 description 65
- 238000007747 plating Methods 0.000 description 36
- 238000012545 processing Methods 0.000 description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 26
- 238000011156 evaluation Methods 0.000 description 22
- 239000010410 layer Substances 0.000 description 21
- 239000011651 chromium Substances 0.000 description 13
- 238000011282 treatment Methods 0.000 description 13
- 238000005096 rolling process Methods 0.000 description 12
- 238000005336 cracking Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000655 Killed steel Inorganic materials 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007564 Zn—Co Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
- H01M50/128—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only inorganic material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/10—Homopolymers or copolymers of propene
- C09D123/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
- C21D9/48—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals deep-drawing sheets
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/121—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
- H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
- H01M50/133—Thickness
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Description
本発明は、リチウムイオン二次電池などの電池容器として好適な金属板およびこの電池容器用金属板の製造方法に関する。 The present invention relates to a metal plate suitable as a battery container for a lithium ion secondary battery and the like, and a method for manufacturing the metal plate for the battery container.
近年における電子機器の小型化は目覚ましく、携帯電話や携帯情報端末などの携帯型電子機器が広く普及している。かような携帯型電子機器においては、その電力源として充電が可能な二次電池が搭載されている。
また、二次電池は、上記した携帯型電子機器に搭載されるに留まらず、ガソリンの枯渇問題や環境問題などが相俟ってハイブリッド自動車や電気自動車などの車両へも徐々に搭載されてきている。
The miniaturization of electronic devices has been remarkable in recent years, and portable electronic devices such as mobile phones and personal digital assistants have become widespread. Such portable electronic devices are equipped with rechargeable secondary batteries as their power source.
In addition, secondary batteries are not only installed in the above-mentioned portable electronic devices, but are also gradually installed in vehicles such as hybrid vehicles and electric vehicles due to problems such as gasoline depletion and environmental problems. There is.
上記した携帯型電子機器あるいは車両に搭載される二次電池においては、高出力で長寿命な高性能電池としてリチウムイオン二次電池（以下、「ＬｉＢ」とも称する）が着目されている。
リチウムイオン二次電池は用途によって様々な種類があり、非水系電解液と正極活物質や負極活物質などを収容する電池容器も円筒形や角型など様々な形態をとる。このうち特許文献１では、薄板状金属板に樹脂を被覆したラミネート金属板を用いたパウチ内に電極などを収容する技術が開示されている。また、この特許文献１によれば、鉄又は鉄の合金を金属箔芯材として用いる旨が言及されている。
Lithium-ion secondary batteries (hereinafter, also referred to as "LiB") are attracting attention as high-performance batteries with high output and long life in the secondary batteries mounted on the above-mentioned portable electronic devices or vehicles.
There are various types of lithium-ion secondary batteries depending on the application, and the battery container that houses the non-aqueous electrolyte solution and the positive electrode active material, the negative electrode active material, etc. also takes various forms such as a cylindrical shape and a square shape. Among these, Patent Document 1 discloses a technique of accommodating an electrode or the like in a pouch using a laminated metal plate in which a thin plate-shaped metal plate is coated with a resin. Further, according to Patent Document 1, it is mentioned that iron or an alloy of iron is used as a metal foil core material.
また、特許文献２や特許文献３では、厚さ２００μｍ以下の圧延金属板を用い、この圧延金属板上にＮｉめっきを施した後で圧延および熱処理を施すことで、この圧延金属板の表面にＮｉおよびＦｅを含む拡散合金層を形成する技術が開示されている。電解液などに対する耐食性向上を図るため圧延金属板上にポリオレフィン系樹脂が形成されることがあるが、この特許文献２によれば上記拡散合金層を用いることで圧延金属板とポリオレフィン系樹脂との密着性を向上させる旨が言及されている。
Further, in
上記した車両や電子機器に搭載可能な二次電池は、高出力であることに加えて高容量であることも要求されている。ここで、単純に容量を増加させるだけでよい場合には、比較的大きな容器に相応の電極活物質を収容すれば事足りるかもしれない。しかしながら特に車両に搭載される二次電池においては、電池自体の重量増は燃費の悪化に即刻でつながるため、高容量を実現するためであっても重量の増加は極力抑制せねばならない。 The secondary batteries that can be mounted on the above-mentioned vehicles and electronic devices are required to have high capacity in addition to high output. Here, if it is sufficient to simply increase the capacity, it may be sufficient to store the corresponding electrode active material in a relatively large container. However, especially in the case of a secondary battery mounted on a vehicle, an increase in the weight of the battery itself immediately leads to deterioration of fuel efficiency, so that the increase in weight must be suppressed as much as possible even in order to realize a high capacity.
可能な限り重量増を避けつつ高容量を実現する手法として、より厳しい条件下における深絞り加工を行って、電池容器の内容量を増加させることが想定される。特に、電池容器における角部（隅）のＲを小さくし、内部に複数枚重ねて収容する板状電極と電池容器の大きさを合わせることにより、電池容量を増加させることが可能となる。しかしながら、上記した特許文献１乃至３を含む従来の技術では、かような深絞り加工に適しているとは言えず改善の余地は大きい。特に電池容器における角部（隅）では、厳しい条件で深絞り加工を行うと基材の割れや樹脂の剥離が顕著となることが判明した。
本発明は上記した課題を一例として解決することを目的としており、例えば圧延金属板を用いて角部のＲが小さい深絞り加工を行う場合でも基材の割れや樹脂の剥離を抑制可能な電池容器用金属板およびこの電池容器用金属板の製造方法を提供することを目的とする。
As a method of achieving high capacity while avoiding weight increase as much as possible, it is assumed that deep drawing under more severe conditions is performed to increase the internal capacity of the battery container. In particular, it is possible to increase the battery capacity by reducing the radius of the corners (corners) of the battery container and matching the size of the battery container with the plate-shaped electrodes that accommodate a plurality of sheets stacked inside. However, the conventional techniques including the above-mentioned Patent Documents 1 to 3 cannot be said to be suitable for such deep drawing, and there is a lot of room for improvement. In particular, it has been found that cracking of the base material and peeling of the resin become remarkable when deep drawing is performed under severe conditions at the corners (corners) of the battery container.
An object of the present invention is to solve the above-mentioned problems as an example. For example, a battery capable of suppressing cracking of a base material and peeling of a resin even when deep drawing is performed using a rolled metal plate with a small radius at a corner. It is an object of the present invention to provide a metal plate for a container and a method for manufacturing the metal plate for a battery container.
上記した課題を解決するため、本発明の電池容器用金属板は、（１）電池容器として用いられる鉄又はＣｒが１０．５％未満の鉄の合金からなる金属板であって、前記金属板は、Ｃが０．０００１〜０．１重量％、Ｓｉが０．００１〜０．５重量％、Ｍｎが０．０１〜１．０重量％、Ｐが０．００１〜０．０５重量％、Ｓが０．０００１〜０．０２重量％、Ａｌが０．０００５〜０．２０重量％およびＮが０．０００１〜０．００４０重量％の成分を含み、
前記金属板の厚みが１０〜１００μｍであり、前記金属板の引張強度が３００〜７００ＭＰａであり、前記金属板の伸びが５〜３５％であり、前記金属板の平面方向と厚み方向における結晶粒径の比が、前記金属板の断面で測定した場合において０ ．８〜８であることを特徴とする。
なお、上記した（１）の電池容器用金属板においては、（２）前記金属板上にＣｒ又はＮｉを含む表面処理層を有することが好ましい。
また、上記した（１）又は（２）の電池容器用金属板においては、（３）前記金属板は熱可塑性樹脂で被覆されていることが好ましい。
To solve the problems described above, the battery container metal sheet of the present invention is a metal plate made of (1) iron or Cr is iron less than 10.5% alloy is used as the battery case, the metal plate C is 0.0001 to 0.1% by weight, Si is 0.001 to 0.5% by weight, Mn is 0.01 to 1.0% by weight, P is 0.001 to 0.05% by weight, S contains 0.0001 to 0.02% by weight, Al contains 0.0005 to 0.20% by weight, and N contains 0.0001 to 0.0040% by weight.
The thickness of the metal plate is 10 to 100 μm, the tensile strength of the metal plate is 300 to 700 MPa, the elongation of the metal plate is 5 to 35%, and the crystal grains in the plane direction and the thickness direction of the metal plate. The diameter ratio is 0 when measured on the cross section of the metal plate. It is characterized by being 8 to 8.
In the above-mentioned (1) metal plate for a battery container, (2) it is preferable to have a surface treatment layer containing Cr or Ni on the metal plate.
Further, in the above-mentioned metal plate for a battery container (1) or (2), it is preferable that (3) the metal plate is coated with a thermoplastic resin.
また、上記した（３）の電池容器用金属板においては、（４）前記熱可塑性樹脂はポリオレフィン系樹脂又はポリエステル系樹脂を含むことが好ましい。
また、上記した（４）の電池容器用金属板においては、（５）前記ポリオレフィン系樹脂又はポリエステル系樹脂は、前記金属板の両面を被覆することが好ましい。
また、上記した（５）の電池容器用金属板においては、（６）前記金属板のうち一方の面を被覆する前記ポリオレフィン系樹脂はポリプロピレン樹脂であり、前記金属板のうち他方の面を被覆する前記ポリエステル系樹脂はポリエチレンテレフタレート樹脂であることが好ましい。
Further, in the metal plate for a battery container described in (3) described above, it is preferable that the thermoplastic resin (4) contains a polyolefin-based resin or a polyester-based resin.
Further, in the above-mentioned metal plate for a battery container (4), it is preferable that (5) the polyolefin-based resin or the polyester-based resin covers both sides of the metal plate.
Further, in the above-mentioned metal plate for a battery container (5), (6) the polyolefin-based resin that covers one surface of the metal plate is a polypropylene resin, and the other surface of the metal plate is coated. The polyester-based resin to be used is preferably a polyethylene terephthalate resin.
また、上記した（６）の電池容器用金属板においては、（７）前記ポリエステル樹脂は無配向であることが好ましい。
また、上記した（３）〜（７）のいずれかに電池容器用金属板においては、（８）前記熱可塑性樹脂の厚みは、１０〜５０μｍであることが好ましい。
Further, in the metal plate for a battery container described in (6) described above, it is preferable that the polyester resin (7) is non-oriented.
Further, in the metal plate for a battery container according to any one of (3) to (7) described above, (8) the thickness of the thermoplastic resin is preferably 10 to 50 μm.
さらに上記した課題を解決するため、本発明の電池容器用金属板の製造方法は、鉄又はＣｒが１０．５％未満の鉄の合金からなる金属板で構成された電池容器用金属板の製造方法であって、前記金属板は、Ｃが０．０００１〜０．１重量％、Ｓｉが０．００１〜０．５重量％、Ｍｎが０．０１〜１．０重量％、Ｐが０．００１〜０．０５重量％、Ｓが０．０００１〜０．０２重量％、Ａｌが０．０００５〜０．２０重量％およびＮが０．０００１〜０．００４０重量％の成分を含み、前記金属板を冷間圧延してその厚みを１０〜１００μｍとする第１工程と、前記第１工程の後に、前記金属板を焼鈍する第２工程を有し、前記金属板の引張強度が３００〜７００ＭＰａ、前記金属板の伸びが５〜３５％ 、且つ前記金属板の断面で測定した場合において前記金属板の平面方向と厚み方向における結晶粒径の比が０．８〜８となるように軟化させることを特徴とする。
なお上記した電池容器用金属板の製造方法においては、前記第１工程の後で、前記第２工程の前または後に、前記金属板に表面処理層を形成する第３工程を有することが好ましい。
Further, in order to solve the above-mentioned problems, the method for manufacturing a metal plate for a battery container of the present invention is for manufacturing a metal plate for a battery container made of a metal plate made of iron or an alloy of iron having a Cr content of less than 10.5%. According to the method, the metal plate has C of 0.0001 to 0.1% by weight, Si of 0.001 to 0.5% by weight, Mn of 0.01 to 1.0% by weight, and P of 0. The metal contains 001 to 0.05% by weight, S is 0.0001 to 0.02% by weight, Al is 0.0005 to 0.20% by weight, and N is 0.0001 to 0.0040% by weight. It has a first step of cold rolling the plate to make its thickness 10 to 100 μm, and a second step of annealing the metal plate after the first step, and the tensile strength of the metal plate is 300 to 700 MPa. The metal plate is softened so that the elongation of the metal plate is 5 to 35% and the ratio of the crystal particle size in the plane direction and the thickness direction of the metal plate is 0.8 to 8 when measured on the cross section of the metal plate. It is characterized by that.
In the above-mentioned method for manufacturing a metal plate for a battery container, it is preferable to have a third step of forming a surface treatment layer on the metal plate after the first step and before or after the second step.
本発明によれば、圧延金属板を用いて角部のＲが小さい深絞り加工を行う場合でも基材の割れや樹脂の剥離を抑制することができる。 According to the present invention, it is possible to suppress cracking of the base material and peeling of the resin even when deep drawing is performed using a rolled metal plate with a small radius at the corners.
以下、図１を用いて本実施形態の電池容器用金属板１について説明する。なお図１においては、便宜上、電池容器用金属板１の厚み方向をＺ方向とし、さらに電池容器用金属板１の圧延方向をＸ方向として説明する。しかしながらこれら方向の定義付けは本発明の権利範囲を減縮するものではない。
＜電池容器用金属板＞
本実施形態に係る電池容器用金属板１は、鉄又は鉄の合金からなる。鉄の合金としては、電池容器の基材として適用可能な種々の鋼板などが例示でき、例えば低炭素アルミキルド鋼（炭素量０．０１〜０．１５重量％）、炭素量が０．００３重量％以下の極低炭素鋼、または、極低炭素鋼にさらにＴｉやＮｂを添加してなる非時効性極低炭素鋼なども含むものとする。
また、本実施形態に係る電池容器用金属板１の厚さは、１０〜１００μｍであり、より好ましくは１５〜６０μｍである。厚みが１０μｍより小さいと、冷間圧延工程においてピンホールが発生する、あるいは板厚勾差が不安定になるなど品質が不安定となりやすい。また、成型工程において割れが発生し、本願の目的とする効果が得られないおそれがある。一方で厚みが１００μｍを超えると、軽量化の効果が得られないからである。
Hereinafter, the metal plate 1 for a battery container of the present embodiment will be described with reference to FIG. In FIG. 1, for convenience, the thickness direction of the metal plate 1 for the battery container will be described as the Z direction, and the rolling direction of the metal plate 1 for the battery container will be described as the X direction. However, the definition of these directions does not diminish the scope of rights of the present invention.
<Metal plate for battery container>
The metal plate 1 for a battery container according to the present embodiment is made of iron or an alloy of iron. Examples of the iron alloy include various steel plates that can be used as the base material of the battery container. For example, low carbon aluminum killed steel (carbon content 0.01 to 0.15% by weight) and carbon content of 0.003% by weight. It also includes the following ultra-low carbon steels, or non-aging ultra-low carbon steels obtained by further adding Ti and Nb to the ultra-low carbon steels.
The thickness of the battery container metal plate 1 according to the present embodiment is 10 to 100 μm, more preferably 15 to 60 μm. If the thickness is smaller than 10 μm, the quality tends to be unstable, such as pinholes occurring in the cold rolling process or the plate thickness gap becoming unstable. In addition, cracks may occur in the molding process, and the desired effect of the present application may not be obtained. On the other hand, if the thickness exceeds 100 μm, the effect of weight reduction cannot be obtained.
ここで、電池容器用金属板１が鉄の合金である場合における成分組成の一例を次に示す。
（Ｃ：０．０００１〜０．１重量％）
Ｃは、電池容器用金属板１の強度を高める元素である。Ｃの含有量が過剰であると強度が上昇し過ぎて圧延性が低下することから、Ｃの含有量の上限値を０．１重量％とする。一方でＣの含有量の下限値は特に制限はないが、コストを考慮してＣの含有量の下限値は０．０００１重量％とする。なお、Ｃの含有量は、より好ましくは０．００１〜０．０１重量％である。
Here, an example of the component composition when the metal plate 1 for the battery container is an alloy of iron is shown below.
(C: 0.0001 to 0.1% by weight)
C is an element that enhances the strength of the metal plate 1 for a battery container. If the C content is excessive, the strength increases too much and the rollability decreases. Therefore, the upper limit of the C content is set to 0.1% by weight. On the other hand, the lower limit of the C content is not particularly limited, but the lower limit of the C content is 0.0001% by weight in consideration of cost. The C content is more preferably 0.001 to 0.01% by weight.
（Ｓｉ：０．００１〜０．５重量％）
Ｓｉは、電池容器用金属板１の強度を高める元素である。Ｓｉの含有量が過剰であると強度が上昇し過ぎて圧延性が低下することから、Ｓｉの含有量の上限値を０．５重量％とする。一方でＳｉの含有量の下限値は特に制限はないが、コストを考慮してＳｉの含有量の下限値は０．００１重量％とする。なお、Ｓｉの含有量は、より好ましくは０．００１〜０．０２重量％である。
(Si: 0.001 to 0.5% by weight)
Si is an element that enhances the strength of the metal plate 1 for a battery container. If the Si content is excessive, the strength increases too much and the rollability decreases. Therefore, the upper limit of the Si content is set to 0.5% by weight. On the other hand, the lower limit of the Si content is not particularly limited, but the lower limit of the Si content is 0.001% by weight in consideration of cost. The Si content is more preferably 0.001 to 0.02% by weight.
（Ｍｎ：０．０１〜１．０重量％）
Ｍｎは、電池容器用金属板１の強度を高める元素である。Ｍｎの含有量が過剰であると強度が上昇し過ぎて圧延性が低下することから、Ｍｎの含有量の上限値を１．０重量％とする。一方でＭｎの含有量の下限値は特に制限はないが、コストを考慮してＭｎの含有量の下限値は０．０１重量％とする。なお、Ｍｎの含有量は、より好ましくは０．０１〜０．５％重量％である。
(Mn: 0.01 to 1.0% by weight)
Mn is an element that enhances the strength of the metal plate 1 for a battery container. If the Mn content is excessive, the strength will increase too much and the rollability will decrease. Therefore, the upper limit of the Mn content is set to 1.0% by weight. On the other hand, the lower limit of the Mn content is not particularly limited, but the lower limit of the Mn content is 0.01% by weight in consideration of cost. The Mn content is more preferably 0.01 to 0.5% by weight.
（Ｐ：０．００１〜０．０５重量％）
Ｐは、電池容器用金属板１の強度を高める元素である。Ｐの含有量が過剰になると強度が上昇し過ぎて圧延性が低下することから、Ｐの含有量の上限値を０．０５重量％とする。一方、Ｐの含有量の下限値は特に制限はないが、コストを考慮してＰの含有量の下限値は０．００１重量％とする。なお、Ｐの含有量は、より好ましくは０．００１〜０．０２重量％である。
(P: 0.001 to 0.05% by weight)
P is an element that enhances the strength of the metal plate 1 for a battery container. If the P content becomes excessive, the strength increases too much and the rollability decreases. Therefore, the upper limit of the P content is set to 0.05% by weight. On the other hand, the lower limit of the P content is not particularly limited, but the lower limit of the P content is 0.001% by weight in consideration of cost. The content of P is more preferably 0.001 to 0.02% by weight.
（Ｓ：０．０００１〜０．０２重量％）
Ｓは、電池容器用金属板１の耐腐食性を低下させる元素である。そのため、Ｓの含有量は少ないほど好ましい。特に、Ｓの含有量が０．０２重量％を超えると耐腐食性の低下が顕著となることから、Ｓの含有量の上限値を０．０２重量％とする。一方でＳの含有量の下限値は特に制限はないが、コストを考慮してＳの含有量の下限値は０．０００１重量％とする。なお、Ｓの含有量は、より好ましくは０．００１〜０．０１重量％である。
(S: 0.0001 to 0.02% by weight)
S is an element that lowers the corrosion resistance of the metal plate 1 for a battery container. Therefore, the smaller the S content, the more preferable. In particular, when the S content exceeds 0.02% by weight, the corrosion resistance is significantly reduced. Therefore, the upper limit of the S content is set to 0.02% by weight. On the other hand, the lower limit of the S content is not particularly limited, but the lower limit of the S content is 0.0001% by weight in consideration of cost. The content of S is more preferably 0.001 to 0.01% by weight.
（Ａｌ：０．０００５〜０．２０重量％）
Ａｌは、例えば電池容器用金属板１の脱酸元素として添加される。脱酸による効果を得るためには、Ａｌの含有量を０．０００５重量％以上とすることが好ましい。しかしながら、Ａｌの含有量が過剰になると圧延性が低下することから、Ａｌの含有量の上限値を０．２０重量％とする。一方で、Ａｌの含有量の下限値は特に制限はないが、コストを考慮してＡｌの含有量の下限値は０．０００５重量％とする。なお、Ａｌの含有量は、より好ましくは０．００１〜０．１０％である。
(Al: 0.0005 to 0.20% by weight)
Al is added, for example, as a deoxidizing element of the metal plate 1 for a battery container. In order to obtain the effect of deoxidation, the Al content is preferably 0.0005% by weight or more. However, if the Al content becomes excessive, the rollability deteriorates, so the upper limit of the Al content is set to 0.20% by weight. On the other hand, the lower limit of the Al content is not particularly limited, but the lower limit of the Al content is 0.0005% by weight in consideration of cost. The Al content is more preferably 0.001 to 0.10%.
（Ｎ：０．０００１〜０．００４０重量％）
Ｎは、電池容器用金属板１の加工性を低下させる元素である。そのため、Ｎの含有量は少ないほど好ましい。特に、Ｎの含有量が０．００４０重量％を超えると加工性の低下が顕著となることから、Ｎの含有量の上限値を０．００４０重量％とする。一方でＮの含有量の下限値は特に制限はないが、コストを考慮してＮの含有量の下限値は０．０００１重量％とする。なお、Ｎの含有量は、より好ましくは０．００１〜０．００４０重量％である。
(N: 0.0001 to 0.0040% by weight)
N is an element that reduces the workability of the metal plate 1 for a battery container. Therefore, the smaller the N content, the more preferable. In particular, when the N content exceeds 0.0040% by weight, the workability is significantly reduced. Therefore, the upper limit of the N content is set to 0.0040% by weight. On the other hand, the lower limit of the N content is not particularly limited, but the lower limit of the N content is 0.0001% by weight in consideration of cost. The N content is more preferably 0.001 to 0.0040% by weight.
（残部：Ｆｅ及び不可避的不純物）
電池容器用金属板１の残部のうち主要な元素はＦｅであり、その他は製造時に不可避的に混入してしまう不純物である。
(Remaining: Fe and unavoidable impurities)
The main element in the rest of the metal plate 1 for the battery container is Fe, and the other elements are impurities that are inevitably mixed in during manufacturing.
その他、付加成分として、Ｔｉ、Ｎｂ、Ｂ、Ｃｕ、Ｎｉ、Ｓｎ、及びＣｒなどが含有されていてもよい。特にＴｉ及びＮｂは、電池容器用金属板１中のＣ及びＮを炭化物及び窒化物として固定して、電池容器用金属板１の加工性を向上させる効果を有するので、Ｔｉ：０．０１〜０．８重量％、Ｎｂ：０．００５〜０．０５重量％の範囲で１種または２種を含有させてもよい。また、本実施形態に係る電池容器用金属板１はＣｒが１０．５％以下の鋼板がより好ましい。 In addition, Ti, Nb, B, Cu, Ni, Sn, Cr and the like may be contained as additional components. In particular, Ti and Nb have the effect of fixing C and N in the metal plate 1 for the battery container as carbides and nitrides to improve the workability of the metal plate 1 for the battery container. Therefore, Ti: 0.01 to One or two types may be contained in the range of 0.8% by weight and Nb: 0.005 to 0.05% by weight. Further, the metal plate 1 for a battery container according to the present embodiment is more preferably a steel plate having a Cr of 10.5% or less.
なお本実施形態に係る電池容器用金属板１は、冷間圧延された後で焼鈍されることで、以下の特性を備えている。なお、本実施形態の焼鈍に必要な温度と時間は、４５０℃〜６５０℃（より好ましくは５００〜６００℃）で行う場合は２〜９時間、さらに好ましくは２〜６時間である。また、７００〜８００℃で焼鈍を行う場合、その所要時間は２０〜１２０秒である。
（引張強度）
本実施形態に係る電池容器用金属板１の引張強度は、３００〜７００ＭＰａである。引張強度が３００ＭＰａより小さいと、電池容器として用いた際に外部からの力で変形してしまうことにより割れ・孔が発生し、これにより電解液の漏れなどが発生してしまう問題がある。また、引張強度が７００ＭＰａを超えると加工性が乏しくなってしまうためである。なお、電池容器用金属板１の引張強度は、より好ましくは、３５０〜６５０ＭＰａである。より加工性を必要とする場合には、更に好ましくは３５０〜４５０ＭＰａである。
なお電池容器用金属板１の引張強度は、ＪＩＳ規格のＺ２２４１に記載された「金属材料引張試験方法」に準じて行った。
The metal plate 1 for a battery container according to the present embodiment has the following characteristics by being cold-rolled and then annealed. The temperature and time required for annealing of the present embodiment are 2 to 9 hours, more preferably 2 to 6 hours when the annealing is performed at 450 ° C to 650 ° C (more preferably 500 to 600 ° C). Further, when annealing is performed at 700 to 800 ° C., the required time is 20 to 120 seconds.
(Tensile strength)
The tensile strength of the battery container metal plate 1 according to the present embodiment is 300 to 700 MPa. If the tensile strength is less than 300 MPa, when it is used as a battery container, it is deformed by an external force, which causes cracks and holes, which causes a problem that an electrolytic solution leaks. Further, if the tensile strength exceeds 700 MPa, the workability becomes poor. The tensile strength of the battery container metal plate 1 is more preferably 350 to 650 MPa. When more workability is required, it is more preferably 350 to 450 MPa.
The tensile strength of the metal plate 1 for the battery container was set according to the "Metallic Material Tensile Test Method" described in Z2241 of the JIS standard.
（伸び）
本実施形態に係る電池容器用金属板１の伸びは、５〜３５％である。電池容器用金属板１の伸びが５％未満だと角（隅）部において加工性が乏しくなり、加工の際に割れが生じるおそれがあるためである。また、伸びが３６％以上であるとこのような特性を出すための焼鈍条件として高い温度・長い時間が必要となるため、生産性が悪くなるためである。なお、電池容器用金属板の伸びは、より好ましくは、５〜２０％である。特に、電池容器用金属板１の厚みが薄い場合には５〜１５％が好ましく、更に好ましくは７〜１２％である。
なお電池容器用金属板１の伸びは、ＪＩＳ規格のＺ２２４１に記載された「金属材料引張試験方法」の「２０：破断伸び（％）Ａの測定の式（７）」に準じて行った。
(stretch)
The elongation of the battery container metal plate 1 according to the present embodiment is 5 to 35%. This is because if the elongation of the metal plate 1 for the battery container is less than 5%, the workability is poor at the corners, and cracks may occur during processing. Further, when the elongation is 36% or more, a high temperature and a long time are required as annealing conditions for obtaining such characteristics, so that the productivity is deteriorated. The elongation of the metal plate for the battery container is more preferably 5 to 20%. In particular, when the thickness of the metal plate 1 for the battery container is thin, it is preferably 5 to 15%, more preferably 7 to 12%.
The elongation of the metal plate 1 for the battery container was carried out according to "20: Measurement formula (7) of elongation at break (%) A" of "Metallic material tensile test method" described in Z2241 of JIS standard.
（結晶粒径の比）
本実施形態に係る電池容器用金属板１の平面方向（圧延方向）と厚み方向における結晶粒径の比（平面方向／厚み方向）は、０．８〜８である。なお本実施形態の「結晶粒径」は、単位面積（例えば１μｍ×１μｍ）当たりに存在する結晶粒径の平均値である。この平均結晶粒径を測定する方法に特に制限はないが、例えば走査型電子顕微鏡（ＳＥＭ）で金属板の断面写真の撮影を行った上でＪＩＳ Ｇ０５５１（附属書ＢまたはＣ）に準拠して測定することができる。平面方向（圧延方向）と厚み方向における比を求めるには、平面方向に沿った試験線と厚み方向に沿った試験線のそれぞれに基づいて結晶粒径を求め、その比を計算する。なお、測定対象となる複数の粒子それぞれにおいて、圧延方向における最長の長さ値と、厚み方向における最長の長さ値とを対比することで上述した結晶粒径の比を算出してもよい。
電池容器用金属板１の上記した結晶粒径の比が０．８未満となるようなものは一般的な製造方法において困難である。また、上記した結晶粒径の比が８を超えると加工の際に割れが生じやすい。なお、電池容器用金属板１の上記した結晶粒径の比は、より好ましくは０．８〜５である。より加工性が求められる場合、電池容器用金属板１の上記した結晶粒径の比は、更に好適には０．８〜４である。
(Ratio of crystal grain size)
The ratio of the crystal grain size in the plane direction (rolling direction) and the thickness direction (plane direction / thickness direction) of the metal plate 1 for a battery container according to the present embodiment is 0.8 to 8. The "crystal particle size" of the present embodiment is an average value of crystal particle sizes existing per unit area (for example, 1 μm × 1 μm). The method for measuring the average crystal grain size is not particularly limited, but for example, a cross-sectional photograph of a metal plate is taken with a scanning electron microscope (SEM) and then in accordance with JIS G0551 (Annex B or C). Can be measured. To obtain the ratio between the plane direction (rolling direction) and the thickness direction, the crystal grain size is calculated based on each of the test line along the plane direction and the test line along the thickness direction, and the ratio is calculated. The ratio of the crystal grain size described above may be calculated by comparing the longest length value in the rolling direction with the longest length value in the thickness direction for each of the plurality of particles to be measured.
A metal plate 1 for a battery container having a crystal particle size ratio of less than 0.8 is difficult in a general manufacturing method. Further, if the ratio of the crystal grain sizes described above exceeds 8, cracks are likely to occur during processing. The ratio of the above-mentioned crystal grain size of the metal plate 1 for the battery container is more preferably 0.8 to 5. When more processability is required, the ratio of the above-mentioned crystal grain sizes of the metal plate 1 for a battery container is more preferably 0.8 to 4.
＜表面処理層＞
本実施形態に係る電池容器用金属板１上には、表面処理層２が形成されていてもよい。この表面処理層２としては、例えば上に形成される樹脂との密着性向上のためにはＣｒめっき又はＮｉめっきが挙げられ、単層またはこれらを複層させてもよく、これらの上に、あるいはこれらに代えて耐食性向上のための処理層（例えば、Ｎｉ−Ｃｏめっき処理層、ＺｎめっきやＺｎ−Ｎｉ、Ｚｎ−ＣｏめっきなどのＺｎ系めっき処理層、Ｓｎめっき処理層、これらのめっきと下地金属との間の分散めっき処理層、酸化物皮膜を形成する化成処理層、シランカップリング剤処理層など）を設けても良い。なお本実施形態の表面処理層は、例えば電池容器用金属板１が冷間圧延後に焼鈍された後に形成してもよいし、電池容器用金属板１が冷間圧延された後であって焼鈍される前に形成することも可能である。また、図１においては電池容器用金属板１の両面に表面処理層２が形成されているが、少なくとも一方の面に表面処理層２が形成される態様でもよい。
<Surface treatment layer>
The
なお、電池容器用金属板１上にＮｉめっきを施す場合には、冷間圧延した金属板を通常の方法で電解脱脂、酸洗した後、例えば一例として以下に示すＮｉめっき浴を用いることができる。なおＮｉめっき浴としてはワット浴と称される硫酸ニッケル浴が主と用いられるが、この他、スルファミン酸浴、ほうフッ化物浴、塩化物浴などを用いてもよい。
（Ｎｉめっき浴組成、条件）
硫酸ニッケル：２００〜３５０ｇ／ｌ
塩化ニッケル：２０〜６０ｇ／ｌ
ほう酸：１０〜５０ｇ／ｌ
ｐＨ：１．５〜５．０
浴温度：４０〜７０℃
電流密度：１〜４０Ａ／ｄｍ２
When Ni plating is applied to the metal plate 1 for a battery container, the cold-rolled metal plate may be electrolytically degreased and pickled by a usual method, and then, for example, the Ni plating bath shown below may be used. can. As the Ni plating bath, a nickel sulfate bath called a watt bath is mainly used, but in addition, a sulfamic acid bath, a boron fluoride bath, a chloride bath and the like may be used.
(Ni plating bath composition, conditions)
Nickel sulfate: 200-350 g / l
Nickel chloride: 20-60 g / l
Boric acid: 10-50 g / l
pH: 1.5-5.0
Bath temperature: 40-70 ° C
Current density: 1-40A / dm 2
なお、電池容器用金属板１上に形成される表面処理層２は、少なくとも電池容器用金属板１において容器の内面となる面に設ければよいが、容器の外面・内面の両面に形成してもよい。また、電池容器用金属板１上に形成される表面処理層２としてのニッケルめっきは、純粋なＮｉだけでなく、Ｎｉ−Ｃｏ合金や、Ｆｅ−Ｎｉ合金などのようにＮｉを含む合金を用いて形成されたものであってもよい。
また、本実施形態のニッケルめっきの厚みは、好ましくは０．１〜５μｍである。このうち下限の値については、より好ましくは０．３μｍ、さらに好ましくは０．５μｍである。一方で上限の値については、より好ましくは３μｍ、さらに好ましくは１μｍである。
また、表面処理層２としてニッケルめっきを電池容器用金属板１上に形成した後、熱処理を施す場合、Ｆｅ−Ｎｉ拡散層が形成される。加工性向上の観点から、このＦｅ−Ｎｉ拡散層は０．２μｍ以上あることが好ましく、更には０．５μｍ以上の厚みがあるとより好ましい。
The
The thickness of the nickel plating of the present embodiment is preferably 0.1 to 5 μm. Of these, the lower limit value is more preferably 0.3 μm, still more preferably 0.5 μm. On the other hand, the upper limit value is more preferably 3 μm, still more preferably 1 μm.
Further, when nickel plating is formed on the metal plate 1 for a battery container as the
また、電池容器用金属板１上にＣｒめっきを施す場合には、冷間圧延した金属板を通常の方法で電解脱脂、酸洗した後、例えば一例として以下に示すＣｒめっき浴を用いることができる。この場合、表面処理層２としてのＣｒめっきの厚みは、０．０５〜１．０μｍが好適である。
（Ｃｒめっき浴組成、条件）
ＣｒＯ３：３０〜２００ｇ／ｌ
ＮａＦ：５〜１０ｇ／ｌ
浴温度：３５〜６５℃
電流密度：５〜５０Ａ／ｄｍ２
When Cr plating is applied to the metal plate 1 for a battery container, the cold-rolled metal plate may be electrolytically degreased and pickled by a usual method, and then, for example, the Cr plating bath shown below may be used. can. In this case, the thickness of Cr plating as the
(Cr plating bath composition, conditions)
CrO 3 : 30-200 g / l
NaF: 5-10 g / l
Bath temperature: 35-65 ° C
Current density: 5 to 50 A / dm 2
＜熱可塑性樹脂＞
本実施形態に係る電池容器用金属板１は、少なくとも一方の面が熱可塑性樹脂３で被覆されていてもよい。かような熱可塑性樹脂３の厚みは、１０〜５０μｍであり、より好ましくは１０〜３０μｍである。
また、本実施形態の熱可塑性樹脂３としては、ポリオレフィン系樹脂、ポリエステル系樹脂又はポリアミド樹脂が例示される。そしてこのポリオレフィン系樹脂、ポリエステル系樹脂又はポリアミド樹脂は、電池容器用金属板１の両面を被覆していることが好ましい。この場合においては、電池容器用金属板１のうち一方の面（電池缶の内面側）はポリプロピレン樹脂で被覆されることが好ましい。一方で、電池容器用金属板１のうち他方の面（電池缶の外面側）は、ポリエステル樹脂、特にポリエチレンテレフタレートで被覆することが好ましい。なおポリエステル樹脂としては、ポリエチレンテレフタレートの他に例えば、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート等を使用することができる。また、ウレタン変性ポリエステル樹脂、アクリル変性ポリエステル樹脂、エポキシ変性ポリエステル樹脂などの変性樹脂を用いても良い。
<Thermoplastic resin>
At least one surface of the battery container metal plate 1 according to the present embodiment may be coated with the thermoplastic resin 3. The thickness of such a thermoplastic resin 3 is 10 to 50 μm, more preferably 10 to 30 μm.
Moreover, as the thermoplastic resin 3 of this embodiment, a polyolefin-based resin, a polyester-based resin, or a polyamide resin is exemplified. The polyolefin-based resin, polyester-based resin, or polyamide resin preferably covers both sides of the metal plate 1 for a battery container. In this case, it is preferable that one surface (inner surface side of the battery can) of the battery container metal plate 1 is coated with polypropylene resin. On the other hand, it is preferable that the other surface (outer surface side of the battery can) of the battery container metal plate 1 is coated with polyester resin, particularly polyethylene terephthalate. As the polyester resin, for example, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and the like can be used in addition to polyethylene terephthalate. Further, a modified resin such as a urethane-modified polyester resin, an acrylic-modified polyester resin, or an epoxy-modified polyester resin may be used.
なお、電池容器用金属板１のうち一方の面（例えば電池缶の内面側）を被覆する樹脂の厚みと、他方の面（例えば電池缶の外面側）を被覆する樹脂の厚みは、要求される耐食性・加工性により上記厚み範囲の間で適宜調整すればよく、両面の厚みは同じでも異なっていてもよい。
また、ポリエステル樹脂を使用する場合、このポリエステル樹脂は無配向であることが好ましい。
また、電池容器用金属板１のうち他方の面（電池缶の外面側）は、上記したポリエステル樹脂（ポリエチレンテレフタレート）に限られず、電池容器用金属板１の両面共にポリプロピレン樹脂で被覆してもよい。あるいは、電池容器用金属板１の両面共にポリエステル樹脂で被覆してもよい。
The thickness of the resin that covers one surface (for example, the inner surface side of the battery can) and the thickness of the resin that covers the other surface (for example, the outer surface side of the battery can) of the battery container metal plate 1 are required. The thickness may be appropriately adjusted within the above thickness range depending on the corrosion resistance and processability, and the thicknesses on both sides may be the same or different.
When a polyester resin is used, it is preferable that the polyester resin is non-oriented.
Further, the other surface (outer surface side of the battery can) of the metal plate 1 for the battery container is not limited to the polyester resin (polyethylene terephthalate) described above, and both sides of the metal plate 1 for the battery container may be coated with polypropylene resin. good. Alternatively, both sides of the battery container metal plate 1 may be coated with polyester resin.
また、熱可塑性樹脂３は、公知の接着剤を介して電池容器用金属板１を被覆している形態であってもよい。なお公知の接着剤としては、例えば、酸変性ポリオレフィン樹脂、エポキシ樹脂、アクリル樹脂、ウレタン樹脂、シリコン樹脂、ポリイソブチレン系樹脂、フッ素樹脂、或いは水ガラス等の無機接着剤などを用いることができる。
前記熱可塑性樹脂３は、フィルムを形成した後に前記電池容器用金属板１にラミネートするものであってもよいし、加熱溶融した前記熱可塑性樹脂を押し出し成形機の押し出し幅のスリットによってフィルム状に押し出し、直接金属板１上にラミネートする押し出しラミネート法によるものであってもよい。上記フィルムを形成した後でラミネートする場合、上記フィルムとしては特に限定されず、たとえば、無延伸フィルムであっても一軸延伸フィルムであっても二軸延伸フィルムであってもよい。
Further, the thermoplastic resin 3 may be in the form of coating the metal plate 1 for a battery container with a known adhesive. As the known adhesive, for example, an acid-modified polyolefin resin, an epoxy resin, an acrylic resin, a urethane resin, a silicon resin, a polyisobutylene resin, a fluororesin, an inorganic adhesive such as water glass, or the like can be used.
The thermoplastic resin 3 may be one that is laminated on the metal plate 1 for a battery container after forming a film, or the thermoplastic resin that has been heated and melted is formed into a film by a slit of an extrusion width of an extrusion molding machine. It may be extruded and laminated directly on the metal plate 1 by an extruded laminating method. When laminating after forming the film, the film is not particularly limited, and may be, for example, a non-stretched film, a uniaxially stretched film, or a biaxially stretched film.
＜電池容器用金属板の製造方法＞
次いで、図２を参照しつつ本実施形態の電池容器用金属板の製造方法について説明する。
まず、鉄又は鉄の合金からなる金属板を準備し、プレス加工を行う圧延機に当該金属板を投入することによって冷間圧延を行う（ステップ１）。これにより、厚さが１０〜１００μｍの冷間圧延された電池容器用金属板１が形成される。この冷間圧延は必要に応じて多段階で行ってもよく、間に熱処理を行ってもよい。
<Manufacturing method of metal plate for battery container>
Next, a method of manufacturing the metal plate for the battery container of the present embodiment will be described with reference to FIG.
First, a metal plate made of iron or an iron alloy is prepared, and cold rolling is performed by putting the metal plate into a rolling mill to be pressed (step 1). As a result, a cold-rolled metal plate 1 for a battery container having a thickness of 10 to 100 μm is formed. This cold rolling may be carried out in multiple stages, if necessary, and heat treatment may be carried out in between.
次いで、電池容器用金属板１に対して焼鈍処理を行う（ステップ２）。このとき、焼鈍処理における電池容器用金属板１の温度は、４５０℃〜６５０℃、より好ましくは５００〜６００℃である。また、この焼鈍処理における所要時間は、２〜９時間、より好ましくは２〜６時間行われる。また、７００〜８００℃で焼鈍処理を行う場合は２０〜１２０秒で行うこともできるが、加工性向上の観点から前者の温度範囲で行うのが好ましい。 Next, the metal plate 1 for the battery container is annealed (step 2). At this time, the temperature of the metal plate 1 for the battery container in the annealing treatment is 450 ° C. to 650 ° C., more preferably 500 to 600 ° C. The time required for this annealing treatment is 2 to 9 hours, more preferably 2 to 6 hours. Further, when the annealing treatment is performed at 700 to 800 ° C., it can be performed in 20 to 120 seconds, but it is preferably performed in the former temperature range from the viewpoint of improving workability.
ステップ２の後、好適には電池容器用金属板１に表面処理（めっき処理）を施して当該電池容器用金属板１上に表面処理層２を形成する（ステップ３）。このとき、例えば電池容器用金属板１上には表面処理層２としてＮｉめっき層が形成される。
なお、ステップ３で形成される表面処理層２の厚みとしては、例えばＮｉめっき層であれば０．１〜５μｍ、Ｃｒめっき層であれば０．０５〜１．０μｍが好適である。なお、ステップ２の焼鈍は表面処理層２を形成した後に行ってもよい。また、ステップ２の焼鈍を行った後で表面処理層２を形成した後に、例えばＮｉめっき層の加工性向上を狙いとして熱処理をさらに施してもよい。このＮｉめっき後の熱処理条件としては、ステップ２で記載される焼鈍条件と同様の条件で行うことが可能である。
なお、ステップ１の圧延工程をめっき処理の後に行うと、Ｎｉめっき皮膜の表面にクラックが生じて密着性、耐食性が低下する可能性があり、好ましくない。
After
The thickness of the
If the rolling step of step 1 is performed after the plating treatment, cracks may occur on the surface of the Ni plating film and the adhesion and corrosion resistance may decrease, which is not preferable.
なお、ステップ２、３を経た後の電池容器用金属板１は、引張強度が３００〜７００ＭＰａ、伸びが５〜３５％、且つ電池容器用金属板１の平面方向（圧延方向）と厚み方向における結晶粒径の比が０．８〜８という特性を備えている。
After the
次にステップ４では、表面処理層２が形成された電池容器用金属板１に対して、上記で説明した熱可塑性樹脂３を１０〜５０μｍ程度の厚みで被覆する処理（樹脂被覆処理）を行う。より具体的には、電池容器用金属板１のうち容器内面側となる一方の面にはポリプロピレン樹脂を形成するとともに、容器外面側となる一方の面にはポリエチレンテレフタレート樹脂又はポリプロピレン樹脂を形成する。樹脂の形成方法としては、上述したように、フィルムラミネートでも良いし、押し出しラミネートによる方法でも良い。なお、この熱可塑性樹脂３を被覆する際の電池容器用金属板１の温度は、２００〜２８０℃に調整される。
Next, in step 4, the metal plate 1 for the battery container on which the
そしてステップ５では、深絞り加工を行って、電池容器用金属板１を図４に示すような容器形状に成形する。より具体的には、本実施形態の容器形状は、矩形の電極板が収容可能なように四隅に曲率半径Ｒの隅部が形成された深さＤの矩形状の凹部を有している。なお、図４の容器では四隅のＲが等しくなっているが、この四隅のＲはそれぞれ異なった値としてもよい。 Then, in step 5, deep drawing is performed to form the metal plate 1 for the battery container into a container shape as shown in FIG. More specifically, the container shape of the present embodiment has a rectangular recess having a depth D in which corners having a radius of curvature R are formed at four corners so that a rectangular electrode plate can be accommodated. In the container of FIG. 4, the Rs of the four corners are equal, but the Rs of the four corners may have different values.
なお電池容器は、電極板や電解液などの電池要素を収容した後で密封されるが、本実施形態の電池容器用金属板１は密封に用いられる電池容器の蓋部材としても適用できる。かような電池容器の構成部材である蓋部材は、図４に示した電池容器本体と同様な収容空間を形成されていてもよいし、平板のまま用いることもできる。また、電池容器の密封に際しては、絞り加工された収容部を有する電池容器本体の周縁のフランジ部で、上記した蓋部材とヒートシールするのが好ましい。この場合、電池容器本体と蓋部材の向かい合う面の被覆樹脂が、ポリプロピレン樹脂同士またはポリエステル樹脂同士のように同種類の樹脂が向き合うよう構成することが好ましい。なお上記した密封方法は一例であってこれに限らず、例えば公知の接着剤を用いてもよい。 The battery container is sealed after accommodating battery elements such as an electrode plate and an electrolytic solution, but the metal plate 1 for a battery container of the present embodiment can also be applied as a lid member of a battery container used for sealing. The lid member, which is a constituent member of such a battery container, may have a storage space similar to that of the battery container main body shown in FIG. 4, or may be used as a flat plate. Further, when sealing the battery container, it is preferable that the flange portion on the peripheral edge of the battery container body having the drawn housing portion is heat-sealed with the above-mentioned lid member. In this case, it is preferable that the coating resin on the facing surface of the battery container body and the lid member is configured such that the same type of resin faces each other, such as polypropylene resins or polyester resins. The above-mentioned sealing method is an example and is not limited to this, and for example, a known adhesive may be used.
本実施形態で得られた電池容器は、上述した本実施形態の電池容器用金属板１を用いて形成されるものであるため、ニッケルめっき金属板またはクロムめっき金属板と、樹脂との密着性が高く、それでいて量産加工性に優れるものであるため、アルカリ電池、ニッケル水素電池、ニッケル・カドミウム電池、リチウムイオン電池など種々の一次電池または二次電池の電池容器として好適に用いることができる。 Since the battery container obtained in the present embodiment is formed by using the battery container metal plate 1 of the present embodiment described above, the adhesion between the nickel-plated metal plate or the chrome-plated metal plate and the resin. Therefore, it can be suitably used as a battery container for various primary batteries or secondary batteries such as alkaline batteries, nickel hydrogen batteries, nickel cadmium batteries, and lithium ion batteries.
次に実施例を挙げて本発明についてより具体的に説明する。まず、後述する実施例または比較例で用いた材料Ｎｏ．Ａ〜材料Ｎｏ．Ｆの電池容器用金属板１の製造条件を、次の表１に記す。 Next, the present invention will be described in more detail with reference to examples. First, the material No. 1 used in Examples or Comparative Examples described later. A ~ Material No. The manufacturing conditions of the metal plate 1 for the battery container of F are shown in Table 1 below.
＜材料Ｎｏ．Ａ＞
材料Ｎｏ．Ａとして、まず基材として下記に示す化学組成を有する低炭素アルミキルド鋼の冷間圧延板（厚さ２５μｍ）を準備した。
Ｃ：０．０４重量％、Ｍｎ：０．３２重量％、Ｓｉ：０．０１重量％、Ｐ：０．０１２重量％、Ｓ：０．０１４重量％、残部：Ｆｅおよび不可避的不純物
<Material No. A>
Material No. As A, first, a cold-rolled low-carbon aluminum killed steel plate (thickness 25 μm) having the following chemical composition was prepared as a base material.
C: 0.04% by weight, Mn: 0.32% by weight, Si: 0.01% by weight, P: 0.012% by weight, S: 0.014% by weight, balance: Fe and unavoidable impurities
次に、準備した基材について、電解脱脂、硫酸浸漬の酸洗を行った後、下記条件にてＮｉめっきを行って厚さ１．０μｍの表面処理（Ｎｉめっき）層２を形成した。なお、Ｎｉめっきの条件は、以下の通りとした。
（ニッケルめっきの条件）
浴組成：硫酸ニッケル、塩化ニッケル、ホウ酸、ピット抑制剤
ｐＨ：４．０〜４．６
浴温：６０℃
電流密度：２５〜３０Ａ／ｄｍ２
Next, the prepared base material was subjected to electrolytic degreasing and pickling by immersion in sulfuric acid, and then Ni-plated under the following conditions to form a surface-treated (Ni-plated)
(Conditions for nickel plating)
Bath composition: Nickel sulfate, nickel chloride, boric acid, pit suppressant pH: 4.0-4.6
Bath temperature: 60 ° C
Current density: 25 to 30 A / dm 2
Ｎｉめっき層が形成された基材に対し、焼鈍を６００℃で３時間行うことで、以下の特性を有する電池容器用金属板１を得た。
・引張強度：３９０ＭＰａ
・伸び：１０％
・平面（圧延）方向と厚み方向の結晶粒径の比：１．２
なお、結晶粒径は、図３及び図５に示すように、走査型電子顕微鏡（ＳＥＭ）で電池容器用金属板１の断面写真の撮影を行った上でＪＩＳ Ｇ０５５１（附属書Ｃ）に準拠して、平面方向及び厚み方向のそれぞれについて測定した。
The base material on which the Ni plating layer was formed was annealed at 600 ° C. for 3 hours to obtain a metal plate 1 for a battery container having the following characteristics.
-Tensile strength: 390 MPa
・ Growth: 10%
-Ratio of crystal grain size in the plane (rolling) direction and the thickness direction: 1.2
As shown in FIGS. 3 and 5, the crystal grain size conforms to JIS G0551 (Annex C) after taking a cross-sectional photograph of the metal plate 1 for a battery container with a scanning electron microscope (SEM). Then, measurements were made in each of the plane direction and the thickness direction.
材料Ｎｏ．Ｂ〜Ｅに関しては、材料Ｎｏ．Ａと同じ基材を用い、上記めっき条件と熱処理条件を以下のとおり変えて材料Ｎｏ．Ｂ〜Ｅをそれぞれ用意した。 Material No. Regarding B to E, the material No. Using the same base material as A, the plating conditions and heat treatment conditions were changed as follows to obtain the material No. B to E were prepared respectively.
＜材料Ｎｏ．Ｂ＞
材料Ｎｏ．Ｂでは、材料Ｎｏ．Ａのニッケルめっき層の代わりに、以下の条件で厚さ０．１μｍの表面処理層２としてのＣｒめっき層を形成した。
（クロムめっきの条件）
クロムめっき浴： ＣｒＯ３：１００ｇ／ｌ、ＮａＦ：５ｇ／ｌ
浴温度：４０℃、
電流密度：５０Ａ／ｄｍ２
<Material No. B>
Material No. In B, the material No. Instead of the nickel plating layer of A, a Cr plating layer as a
(Conditions for chrome plating)
Chromium plating bath: CrO 3 : 100 g / l, NaF: 5 g / l
Bath temperature: 40 ° C,
Current density: 50A / dm 2
その後、材料Ｎｏ．Ａと同様に６００℃の温度で３時間の条件で焼鈍を行い、以下の特性を有する電池容器用金属板１を得た。
・引張強度：３９０ＭＰａ
・伸び：１０％
・平面（圧延）方向と厚み方向の結晶粒径の比：１．２
After that, the material No. Annealing was carried out at a temperature of 600 ° C. for 3 hours in the same manner as in A to obtain a metal plate 1 for a battery container having the following characteristics.
-Tensile strength: 390 MPa
・ Growth: 10%
-Ratio of crystal grain size in the plane (rolling) direction and the thickness direction: 1.2
＜材料Ｎｏ．Ｃ＞
材料Ｎｏ．Ｃでは、焼鈍条件を５５０℃の温度で３時間とした以外は、材料Ｎｏ．Ａと同様にして、以下の特性を有する電池容器用金属板１を得た。
・引張強度：３９０ＭＰａ
・伸び：１１％
・平面（圧延）方向と厚み方向の結晶粒径の比：３
<Material No. C>
Material No. In C, except that the annealing condition was set to a temperature of 550 ° C. for 3 hours, the material No. In the same manner as in A, a metal plate 1 for a battery container having the following characteristics was obtained.
-Tensile strength: 390 MPa
・ Growth: 11%
-Ratio of crystal grain size in the plane (rolling) direction and the thickness direction: 3
＜材料Ｎｏ．Ｄ＞
材料Ｎｏ．Ｄでは、焼鈍条件を４５０℃の温度で３時間とした以外は、材料Ｎｏ．Ａと同様にして、以下の特性を有する電池容器用金属板１を得た。
・引張強度：６３０ＭＰａ
・伸び：５．５％
・平面（圧延）方向と厚み方向の結晶粒径の比：５
<Material No. D>
Material No. In D, except that the annealing condition was set to a temperature of 450 ° C. for 3 hours, the material No. In the same manner as in A, a metal plate 1 for a battery container having the following characteristics was obtained.
-Tensile strength: 630 MPa
・ Growth: 5.5%
-Ratio of crystal grain size in the plane (rolling) direction and the thickness direction: 5
＜材料Ｎｏ．Ｅ＞
材料Ｎｏ．Ｅでは、焼鈍条件を行わなかった以外は材料Ｎｏ．Ａと同様にして、以下の特性を有する電池容器用金属板１を得た。
・引張強度：７８０ＭＰａ
・伸び：３％
・平面（圧延）方向と厚み方向の結晶粒径の比：１０
<Material No. E>
Material No. In E, the material No. was not subjected to the annealing conditions. In the same manner as in A, a metal plate 1 for a battery container having the following characteristics was obtained.
-Tensile strength: 780 MPa
・ Growth: 3%
-Ratio of crystal grain size in the plane (rolling) direction and the thickness direction: 10
＜材料Ｎｏ．Ｆ＞
材料Ｎｏ．Ｆでは、下記の組成を有する厚み２５μｍの純アルミニウム板（ＪＩＳ Ｈ４０００合金番号Ａ１０５０のＯ材）を、表面処理層を設けず、焼鈍処理を行わずに、電池容器用金属板１として用いた。
<Material No. F>
Material No. In F, a pure aluminum plate having the following composition and a thickness of 25 μm (O material of JIS H4000 alloy number A1050) was used as the metal plate 1 for a battery container without providing a surface treatment layer and without annealing treatment.
この材料Ｎｏ．Ｆの特性は次に示すとおりである。なお材料Ｎｏ．Ｆについては、結晶粒径の測定は行わなかった。
・引張強度：６０ＭＰａ
・伸び：５％
This material No. The characteristics of F are as shown below. In addition, material No. For F, the crystal grain size was not measured.
-Tensile strength: 60 MPa
・ Growth: 5%
次いで、このようにして得られた材料Ｎｏ．Ａ〜材料Ｎｏ．Ｆを用いた電池容器用金属板１に対し、電池容器用金属板１のうち容器内面側となる一方の面にはポリプロピレン樹脂を形成するとともに、容器外面側となる一方の面にはポリエチレンテレフタレート樹脂をそれぞれ形成した。なお、このときのラミネート温度（電池容器用金属板１の温度）は、２６０℃とした。 Next, the material No. obtained in this way. A ~ Material No. In contrast to the metal plate 1 for a battery container using F, polypropylene resin is formed on one surface of the metal plate 1 for a battery container that is on the inner surface side of the container, and polyethylene terephthalate is formed on one surface that is on the outer surface side of the container. Resins were formed respectively. The lamination temperature (the temperature of the metal plate 1 for the battery container) at this time was set to 260 ° C.
（電池容器への加工）
上記のごとく両面に熱可塑性樹脂３が形成された電池容器用金属板１に対し、図４に示すように、外形寸法を縦Ｈ＝７０ｍｍ×横Ｗ＝７０ｍｍ、電池容器の四隅における曲率半径Ｒを１２．５、１５、２０および２５ｍｍとしてそれぞれ加工した。このとき、深さＤを４〜１７ｍｍの範囲で絞り加工を行って電池容器を形成した。
なお、電池容器への加工に際しては、絞り加工の深さをＤ、曲率半径Ｒとした場合、Ｄ／Ｒの値が重要となることが判明した。より具体的には、Ｄ／Ｒの値が大きいほど加工が厳しくなるが、より容量の大きい電池容器の形成が可能となる。かような知見に基づけば、Ｄ／Ｒの値は、好ましくは０．４以上、より好ましくは０．９以上である。これにより電池容器としての容量を大きくすることができる。
(Processing into a battery container)
As shown in FIG. 4, the external dimensions of the metal plate 1 for a battery container in which the thermoplastic resin 3 is formed on both sides as described above are: vertical H = 70 mm × horizontal W = 70 mm, and the radius of curvature R at the four corners of the battery container. Was processed as 12.5, 15, 20 and 25 mm, respectively. At this time, the battery container was formed by drawing the depth D in the range of 4 to 17 mm.
It was found that the value of D / R is important when the depth of drawing is D and the radius of curvature is R when processing the battery container. More specifically, the larger the D / R value, the more severe the processing, but it is possible to form a battery container having a larger capacity. Based on such findings, the D / R value is preferably 0.4 or more, more preferably 0.9 or more. As a result, the capacity of the battery container can be increased.
（加工後の評価方法）
加工後の評価は、電池容器の四隅で基材の割れや熱可塑性樹脂の浮きや割れを目視にて観察して評価した。
なお評価は以下の基準で行った（後述の他の実施例や比較例も同様）。
［評価基準］
３点：目視で判定した結果、基材の割れや熱可塑性樹脂の浮き／割れが認められなかった。
２点：目視で判定した結果、実用には供せるが一部に割れや浮きが認められた。
１点：目視で判定した結果、実用に供せない程度の基材の割れや熱可塑性樹脂の浮き／割れが認められた。
(Evaluation method after processing)
The evaluation after processing was carried out by visually observing cracks in the base material and floating and cracking of the thermoplastic resin at the four corners of the battery container.
The evaluation was performed according to the following criteria (the same applies to other examples and comparative examples described later).
[Evaluation criteria]
3 points: As a result of visual judgment, no cracking of the base material or floating / cracking of the thermoplastic resin was observed.
2 points: As a result of visual judgment, cracks and floats were found in some parts, although they could be used for practical purposes.
1 point: As a result of visual judgment, cracking of the base material and floating / cracking of the thermoplastic resin were observed to the extent that it could not be put into practical use.
＜実施例１＞
電池容器用金属板１として表１に示す材料Ｎｏ．Ａを用いた。そしてこの電池容器用金属板１のうち容器内面側となる一方の面にはポリプロピレン樹脂を厚さ３０μｍで形成するとともに、容器外面側となる一方の面にはポリエチレンテレフタレート樹脂を厚さ１２μｍでそれぞれ形成した。なお、このときのラミネート温度（電池容器用金属板１の温度）は、２６０℃とした。
そして絞り加工時の深さを１１ｍｍとして電池容器への加工を行った。
この実施例１における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Example 1>
The material No. 1 shown in Table 1 as the metal plate 1 for the battery container. A was used. Then, polypropylene resin is formed with a thickness of 30 μm on one surface of the metal plate 1 for a battery container on the inner surface side of the container, and polyethylene terephthalate resin is formed on one surface on the outer surface side of the container with a thickness of 12 μm. Formed. The lamination temperature (the temperature of the metal plate 1 for the battery container) at this time was set to 260 ° C.
Then, the battery container was processed with a depth of 11 mm at the time of drawing.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Example 1.
＜実施例２＞
絞り加工時の深さを１５ｍｍとした以外は、実施例１と同様に行った。
この実施例２における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Example 2>
The same procedure as in Example 1 was carried out except that the depth at the time of drawing was set to 15 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Example 2.
＜実施例３＞
絞り加工時の深さを１７ｍｍとした以外は、実施例１と同様に行った。
この実施例３における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Example 3>
The same procedure as in Example 1 was carried out except that the depth at the time of drawing was set to 17 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Example 3.
＜実施例４＞
電池容器の外面側に形成されるポリエチレンテレフタレート樹脂の厚みを３０μｍとし、絞り加工時の深さを１７ｍｍとした以外は、実施例１と同様に行った。
この実施例４における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Example 4>
The same procedure as in Example 1 was carried out except that the thickness of the polyethylene terephthalate resin formed on the outer surface side of the battery container was 30 μm and the depth during drawing was 17 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Example 4.
＜実施例５＞
電池容器の内面側に形成されるポリプロピレン樹脂の厚みを２０μｍ、電池容器の外面側に形成されるポリエチレンテレフタレート樹脂の厚みを３０μｍとし、絞り加工時の深さを１７ｍｍとした以外は、実施例１と同様に行った。
この実施例５における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Example 5>
Example 1 except that the thickness of the polypropylene resin formed on the inner surface side of the battery container is 20 μm, the thickness of the polyethylene terephthalate resin formed on the outer surface side of the battery container is 30 μm, and the depth at the time of drawing is 17 mm. I went in the same way.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Example 5.
＜実施例６＞
電池容器用金属板として表１に示す材料Ｎｏ．Ｂを用い、絞り加工時の深さを１７ｍｍとした以外は、実施例１と同様に行った。
この実施例６における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Example 6>
Material No. 1 shown in Table 1 as a metal plate for a battery container. The same procedure as in Example 1 was carried out except that B was used and the depth at the time of drawing was 17 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Example 6.
＜実施例７＞
電池容器用金属板として表１に示す材料Ｎｏ．Ｃを用いた以外は、実施例１と同様に行った。
この実施例７における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Example 7>
Material No. 1 shown in Table 1 as a metal plate for a battery container. The procedure was the same as in Example 1 except that C was used.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Example 7.
＜実施例８＞
電池容器用金属板として表１に示す材料Ｎｏ．Ｄを用い、絞り加工時の深さを５ｍｍとした以外は、実施例１と同様に行った。
この実施例８における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Example 8>
Material No. 1 shown in Table 1 as a metal plate for a battery container. The same procedure as in Example 1 was carried out except that D was used and the depth at the time of drawing was set to 5 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Example 8.
＜実施例９＞
絞り加工時の深さを６ｍｍとした以外は、実施例８と同様に行った。
この実施例９における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Example 9>
The same procedure as in Example 8 was carried out except that the depth at the time of drawing was set to 6 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Example 9.
＜実施例１０＞
絞り加工時の深さを７ｍｍとした以外は、実施例８と同様に行った。
この実施例１０における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Example 10>
The same procedure as in Example 8 was carried out except that the depth at the time of drawing was 7 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Example 10.
＜実施例１１＞
絞り加工時の深さ１１ｍｍとした以外は、実施例８と同様に行った。
この実施例１１における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Example 11>
The same procedure as in Example 8 was carried out except that the depth at the time of drawing was 11 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Example 11.
＜比較例１＞
電池容器用金属板として表１に示す材料Ｎｏ．Ｅを用い、絞り加工時の深さを４ｍｍとした以外は、実施例１と同様に行った。
この比較例１における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Comparative example 1>
Material No. 1 shown in Table 1 as a metal plate for a battery container. The same procedure as in Example 1 was carried out except that E was used and the depth at the time of drawing was set to 4 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Comparative Example 1.
＜比較例２＞
絞り加工時の深さを５ｍｍとした以外は、比較例１と同様に行った。
この比較例２における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Comparative example 2>
The same procedure as in Comparative Example 1 was carried out except that the depth at the time of drawing was set to 5 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Comparative Example 2.
＜比較例３＞
絞り加工時の深さを６ｍｍとした以外は、比較例１と同様に行った。
この比較例３における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Comparative example 3>
The same procedure as in Comparative Example 1 was carried out except that the depth at the time of drawing was set to 6 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Comparative Example 3.
＜比較例４＞
電池容器の外面側に形成される樹脂を厚さ１９μｍの延伸ポリエチレンテレフタレート樹脂とし、絞り加工時の深さを５ｍｍとした以外は、比較例１と同様に行った。
この比較例４における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Comparative example 4>
The same procedure as in Comparative Example 1 was carried out except that the resin formed on the outer surface side of the battery container was a stretched polyethylene terephthalate resin having a thickness of 19 μm and the depth at the time of drawing was 5 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Comparative Example 4.
＜比較例５＞
電池容器用金属板として表１に示す材料Ｎｏ．Ｆを用いた以外は、比較例１と同様に行った。
この比較例５における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Comparative example 5>
Material No. 1 shown in Table 1 as a metal plate for a battery container. The procedure was the same as in Comparative Example 1 except that F was used.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Comparative Example 5.
＜比較例６＞
絞り加工時の深さを５ｍｍとした以外は、比較例５と同様に行った。
この比較例６における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Comparative Example 6>
The same procedure as in Comparative Example 5 was carried out except that the depth at the time of drawing was set to 5 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Comparative Example 6.
＜比較例７＞
絞り加工時の深さを６ｍｍとした以外は、比較例５と同様に行った。
この比較例７における材料仕様、絞り加工条件および加工結果の評価を表２に示す。
<Comparative Example 7>
The same procedure as in Comparative Example 5 was carried out except that the depth at the time of drawing was set to 6 mm.
Table 2 shows the material specifications, drawing conditions, and evaluation of processing results in Comparative Example 7.
表２に示すように、実施例１〜１１では電池缶の四隅で良好な加工結果を得ることができた。これは、電解液に対する耐食性や樹脂と基材との密着性を確保しつつ電池容器のうち発電要素（電極板、スペーサ、電解液など）が収容される空間を最大限確保できることを意味する。
一方で比較例１〜７では特に曲率半径が小さいほど加工結果は悪化しており、実用に耐えるだけの特性を備えていないことが判明した。
As shown in Table 2, in Examples 1 to 11, good processing results could be obtained at the four corners of the battery can. This means that the space in the battery container in which the power generation elements (electrode plate, spacer, electrolytic solution, etc.) are accommodated can be secured as much as possible while ensuring the corrosion resistance to the electrolytic solution and the adhesion between the resin and the base material.
On the other hand, in Comparative Examples 1 to 7, it was found that the processing result deteriorated as the radius of curvature became smaller, and the characteristics were not sufficient to withstand practical use.
また、本発明者らは、絞り加工の深さＤと電池缶の四隅における曲率半径Ｒとの関係に着目し、これらの比（絞り加工の深さＤと曲率半径Ｒの比（Ｄ／Ｒ））について考察した。Ｄ／Ｒは加工の度合を表すことができ、深さＤが大きいほど、また、Ｒが小さいほど、つまりＤ／Ｒが大きいほど加工は厳しくなる。そして曲率半径Ｒを変化させた場合（Ｒ１２．５、Ｒ１５、Ｒ２０およびＲ２５）におけるこれら比（Ｄ／Ｒ）について下記に示す表３にまとめた。
また、実施例１〜１１および比較例１〜７で用いた電池容器用金属板のトータルの厚み（μｍ）と、絞り加工の深さと曲率半径Ｒの比（Ｄ／Ｒ）との比（トータル板厚／絞り加工の深さＤと曲率半径Ｒの比）についても表３にまとめた。
Further, the present inventors have focused on the relationship between the drawing depth D and the radius of curvature R at the four corners of the battery can, and these ratios (the ratio of the drawing depth D to the radius of curvature R (D / R). )) Was considered. The D / R can express the degree of processing, and the larger the depth D and the smaller the R, that is, the larger the D / R, the more severe the processing. Then, these ratios (D / R) when the radius of curvature R is changed (R12.5, R15, R20 and R25) are summarized in Table 3 shown below.
Further, the ratio (total) of the total thickness (μm) of the metal plate for the battery container used in Examples 1 to 11 and Comparative Examples 1 to 7 and the ratio (D / R) of the drawing depth and the radius of curvature R. Table 3 also summarizes the plate thickness / ratio of drawing depth D and radius of curvature R).
この表３に基づけば、本発明においては以下の特徴を具備しているということができる。
（ａ）同一板厚においては、実施例で規定した条件では、絞り加工の深さＤと曲率半径Ｒとの比（Ｄ／Ｒ）が０．４以上でも加工が可能であり、実施例３〜６においては少なくとも１．４のＤ／Ｒが可能であることが実証されたものである。このことは、例えば電池容器の隅部における曲率半径Ｒが５ｍｍの容器形状の場合、絞り加工の深さＤが７ｍｍ程度まで成形可能であることを示唆する。一方で、比較例で規定した条件では、絞り加工の深さと曲率半径Ｒとの比（Ｄ／Ｒ）は０．３が限界となる。
Based on this Table 3, it can be said that the present invention has the following features.
(A) With the same plate thickness, under the conditions specified in Example, processing is possible even if the ratio (D / R) of the drawing depth D to the radius of curvature R is 0.4 or more, and processing is possible in Example 3. In ~ 6, it was proved that a D / R of at least 1.4 is possible. This suggests that, for example, in the case of a container shape in which the radius of curvature R at the corner of the battery container is 5 mm, the drawing depth D can be formed up to about 7 mm. On the other hand, under the conditions specified in the comparative example, the ratio (D / R) of the drawing depth to the radius of curvature R is limited to 0.3.
（ｂ）トータル板厚と絞り加工の深さと曲率半径Ｒとの比（Ｄ／Ｒ）との関係においては、実施例で規定した条件では、少なくとも０．０５以上で加工が可能であることが実証された。一方で、比較例で規定した条件では、０．２８以上でないと加工が困難となる。 (B) Regarding the relationship between the total plate thickness, the depth of drawing, and the ratio (D / R) of the radius of curvature R, it is possible to process at least 0.05 or more under the conditions specified in the examples. Demonstrated. On the other hand, under the conditions specified in the comparative example, processing becomes difficult unless it is 0.28 or more.
以上説明したように、本発明の電池容器用金属板およびその製造方法は、圧延金属板を用いて角部の曲率半径Ｒが小さい深絞り加工を行う場合においても良好な特性を示すことができ、電池を使用する幅広い分野の産業への適用が可能である。 As described above, the metal plate for a battery container and the manufacturing method thereof of the present invention can exhibit good characteristics even when deep drawing is performed using a rolled metal plate with a small radius of curvature R at the corners. , Can be applied to a wide range of industries that use batteries.
１ 電池容器用金属板
２ 表面処理層
３ 熱可塑性樹脂
1 Metal plate for
Claims (9)
前記金属板は、Ｃが０．０００１〜０．１重量％、Ｓｉが０．００１〜０．５重量％、Ｍｎが０．０１〜１．０重量％、Ｐが０．００１〜０．０５重量％、Ｓが０．０００１〜０．０２重量％、Ａｌが０．０００５〜０．２０重量％およびＮが０．０００１〜０．００４０重量％の成分を含み、
前記金属板の厚みが１０〜１００μｍであり、
前記金属板の引張強度が３００〜７００ＭＰａであり、
前記金属板の伸びが５〜３５％であり、
前記金属板の平面方向と厚み方向における結晶粒径の比が、前記金属板の断面で測定した場合において０ ．８〜８であることを特徴とする電池容器用金属板。 A metal plate made of an alloy of iron or iron having a Cr content of less than 10.5% used as a battery container.
The metal plate has C of 0.0001 to 0.1% by weight, Si of 0.001 to 0.5% by weight, Mn of 0.01 to 1.0% by weight, and P of 0.001 to 0.05. It contains components of 0.0001 to 0.02% by weight of S, 0.0005 to 0.20% by weight of Al and 0.0001 to 0.0040% by weight of N.
The thickness of the metal plate is 10 to 100 μm.
The tensile strength of the metal plate is 300 to 700 MPa, and the metal plate has a tensile strength of 300 to 700 MPa.
The elongation of the metal plate is 5 to 35%, and the elongation is 5 to 35%.
The ratio of the crystal grain size in the plane direction and the thickness direction of the metal plate is 0 when measured in the cross section of the metal plate. A metal plate for a battery container, which is 8 to 8.
前記金属板のうち他方の面を被覆するポリエステル樹脂はポリエチレンテレフタレートである請求項５に記載の電池容器用金属板。 The polyolefin-based resin that covers one surface of the metal plate is a polypropylene resin.
The metal plate for a battery container according to claim 5, wherein the polyester resin covering the other surface of the metal plate is polyethylene terephthalate.
前記金属板は、Ｃが０．０００１〜０．１重量％、Ｓｉが０．００１〜０．５重量％、Ｍｎが０．０１〜１．０重量％、Ｐが０．００１〜０．０５重量％、Ｓが０．０００１〜０．０２重量％、Ａｌが０．０００５〜０．２０重量％およびＮが０．０００１〜０．００４０重量％の成分を含み、
前記金属板を冷間圧延してその厚みを１０〜１００μｍとする第１工程と、
前記第１工程の後に、前記金属板を焼鈍する第２工程を有し、
前記金属板の引張強度が３００〜７００ＭＰａ、前記金属板の伸びが５〜３５％ 、且つ前記金属板の断面で測定した場合において前記金属板の平面方向と厚み方向における結晶粒径の比が０．８〜８となるように軟化させることを特徴とする電池容器用金属板の製造方法。 A method for manufacturing a metal plate for a battery container, which is made of a metal plate made of an alloy of iron or iron having a Cr content of less than 10.5%.
The metal plate has C of 0.0001 to 0.1% by weight, Si of 0.001 to 0.5% by weight, Mn of 0.01 to 1.0% by weight, and P of 0.001 to 0.05. It contains components of 0.0001 to 0.02% by weight of S, 0.0005 to 0.20% by weight of Al and 0.0001 to 0.0040% by weight of N.
In the first step of cold rolling the metal plate to make the thickness 10 to 100 μm,
After the first step, there is a second step of annealing the metal plate.
The tensile strength of the metal plate is 300 to 700 MPa, the elongation of the metal plate is 5 to 35%, and the ratio of the crystal grain size in the plane direction and the thickness direction of the metal plate is 0 when measured in the cross section of the metal plate. .. A method for manufacturing a metal plate for a battery container, which comprises softening the metal plate so as to be 8 to 8.
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| PCT/JP2017/014429 WO2017179492A1 (en) | 2016-04-13 | 2017-04-07 | Metal sheet for battery container, and method of manufacturing metal sheet for battery container |
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