JP3272866B2 - Surface treated steel sheet for alkaline battery case, alkaline battery case and alkaline battery - Google Patents
Surface treated steel sheet for alkaline battery case, alkaline battery case and alkaline batteryInfo
- Publication number
- JP3272866B2 JP3272866B2 JP11407194A JP11407194A JP3272866B2 JP 3272866 B2 JP3272866 B2 JP 3272866B2 JP 11407194 A JP11407194 A JP 11407194A JP 11407194 A JP11407194 A JP 11407194A JP 3272866 B2 JP3272866 B2 JP 3272866B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- battery case
- steel sheet
- alkaline battery
- plating
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
- 229910000831 Steel Inorganic materials 0.000 title claims description 49
- 239000010959 steel Substances 0.000 title claims description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 121
- 238000007747 plating Methods 0.000 claims description 97
- 229910052759 nickel Inorganic materials 0.000 claims description 60
- 238000010438 heat treatment Methods 0.000 claims description 32
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 claims description 23
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 22
- 238000009792 diffusion process Methods 0.000 claims description 20
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 62
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000003466 welding Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000010960 cold rolled steel Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- -1 and therefore Substances 0.000 description 3
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 description 2
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 150000004782 1-naphthols Chemical class 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910005099 Ni3Sn2 Inorganic materials 0.000 description 1
- 229910003306 Ni3Sn4 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000000155 melt Substances 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
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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
- H01M50/10—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
- H01M50/1243—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the internal coating on the casing
-
- 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
-
- 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
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
- H01M50/133—Thickness
-
- 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
- H01M50/134—Hardness
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はアルカリマンガン電池
（以下アルカリ電池という。）ケース用表面処理鋼板、
その表面処理鋼板をプレス成形して得られたアルカリ電
池ケースおよびアルカリ電池に関するものである。より
詳しくはアルカリ電池などの一次電池やニッケルカドニ
ウム電池などの二次電池でアルカリ液を電解液とする電
池に用いられる材料などに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated steel sheet for an alkaline manganese battery (hereinafter referred to as "alkaline battery") case,
The present invention relates to an alkaline battery case and an alkaline battery obtained by press-forming the surface-treated steel sheet. More specifically, the present invention relates to a material used for a primary battery such as an alkaline battery and a secondary battery such as a nickel cadmium battery using an alkaline solution as an electrolyte.
【０００２】[0002]
【従来の技術】アルカリマンガン電池やニッケルカドミ
ウム電池などで用いられている強アルカリ液を封入する
電池用のケースは、プレス加工後バレルめっきする方法
に替わって、ニッケルめっき鋼帯を電池ケースにプレス
加工する方法が主流となってきた。ところでアルカリマ
ンガン電池やニッケルカドミウム電池などの電池ケース
に、ニッケルめっき鋼帯が使用される理由は、これらの
電池は主として強アルカリ性の水酸化カリウムを電解液
としているため、耐アルカリ腐食性にニッケルめっき鋼
帯が強いこと、電池ケースを外部端子に接続する場合安
定した接触抵抗を有していること、電池製造時各構成部
品を溶接し電池に組立てる際スポット溶接が行われる
が、スポット溶接性にも優れると言う利点からである。2. Description of the Related Art A battery case used for alkaline manganese batteries and nickel cadmium batteries for enclosing a strong alkaline solution is a method in which a nickel-plated steel strip is pressed into a battery case instead of a barrel plating method after press working. Processing methods have become mainstream. The reason why nickel-plated steel strips are used for battery cases such as alkaline manganese batteries and nickel-cadmium batteries is that these batteries mainly use strong alkaline potassium hydroxide as an electrolyte, and therefore, nickel plating is used to prevent nickel corrosion. Strong steel strip, stable contact resistance when connecting battery case to external terminals, spot welding is performed when welding each component at the time of battery manufacture and assembling into battery. Is also superior.
【０００３】[0003]
【発明が解決すべき課題】前述のように、ニッケルめっ
き鋼帯が広く電池用途に使われるようになったが、さら
に耐食性の向上、めっき密着性の向上等を目的としてニ
ッケルめっき後に熱拡散処理を施す方法も採用されてき
た。ニッケルめっき後熱処理することにより、次のよう
な特性の改善が得られる。 （１）耐食性，特に成形加工部の耐食性向上 （２）めっき密着性の向上 （３）スポット溶接性の向上 これらの特性向上と熱処理の関係に言及すれば、耐食性
向上は、熱処理によりニッケルめっき層が軟質化し加工
部の塑性変形にニッケルめっき層が追随でき、めっき層
のクラック生成が抑制される。めっき密着性向上は、熱
処理により鋼素地とニッケルめっき層との境界面に鉄ー
ニッケル拡散層が形成され、該境界面で鋼素地とニッケ
ルめっき層とが冶金学的に強固に結合することによる。
さらに第３点のスポット溶接性向上については、鉄ーニ
ッケル拡散層の形成により電気抵抗が高くなり、スポッ
ト溶接時の発熱が高まり溶接ナゲットが生成しやすくな
ることから、溶接可能範囲が広がり溶接強度が大きくな
ることに起因する。以上述べたように、ニッケルめっき
鋼帯のニッケルめっき後の熱処理の利点は数多くある。As described above, nickel-plated steel strips have been widely used for batteries. However, for the purpose of further improving corrosion resistance and plating adhesion, heat diffusion treatment is performed after nickel plating. Has also been adopted. By performing heat treatment after nickel plating, the following characteristics can be improved. (1) Corrosion resistance, especially the corrosion resistance of the formed part (2) Improvement of plating adhesion (3) Improvement of spot weldability If mention is made of the relationship between these characteristics and heat treatment, the corrosion resistance can be improved by the nickel plating layer by heat treatment. Is softened, the nickel plating layer can follow the plastic deformation of the processed portion, and the generation of cracks in the plating layer is suppressed. The improvement in plating adhesion is due to the fact that an iron-nickel diffusion layer is formed at the interface between the steel substrate and the nickel plating layer by heat treatment, and the steel substrate and the nickel plating layer are strongly metallurgically bonded at the interface.
Regarding the third improvement of spot weldability, the formation of an iron-nickel diffusion layer increases the electric resistance, increases the heat generated during spot welding, and facilitates the formation of a welding nugget. It is caused by becoming larger. As described above, there are many advantages of the heat treatment after the nickel plating of the nickel-plated steel strip.
【０００４】一方問題点として、前述のようにニッケル
めっき層が軟化する結果、耐疵付き性が損なわれること
が上げられる。電池ケース用材料として耐疵付き性が損
なわれることは、輸送取扱中もしくは電池製造工程中に
おいて、ニッケルめっき層が損傷を受け、外観の劣化の
みならず耐食性が著しく損なわれることとなる。このた
め熱拡散処理材は、耐疵付き性の改善の必要性が生じ
た。耐疵付き性の向上の方法として、本出願人は先に
「耐疵付き性Ｎｉめっき鋼板およびその製造法」（特開
平２ー１２９３９５号公報参照）を提案したが、耐疵付
き性の効果は優れるものの、ニッケルーリン合金めっき
のリン含有量の制御が困難であること、さらには電池ケ
ースのスポット溶接強度の低下も問題点となっていた。
このスポット溶接性の劣化は、溶接時の温度上昇時溶接
チップとの接触部で低融点であるニッケルーリンめっき
層が溶融し、溶接付加電流密度が下がるため、十分な溶
接ナゲットの生成が阻害されることが原因である。On the other hand, as a problem, as described above, as a result of softening of the nickel plating layer, scratch resistance is impaired. The impairment of the flaw resistance as a material for a battery case means that the nickel plating layer is damaged during transportation and handling or during the battery manufacturing process, which not only deteriorates the appearance but also significantly impairs the corrosion resistance. For this reason, the heat diffusion treatment material needs to be improved in scratch resistance. As a method of improving the scratch resistance, the present applicant has previously proposed "Scratch-resistant Ni-plated steel sheet and a method for producing the same" (see Japanese Patent Application Laid-Open No. 2-129395). However, it is difficult to control the phosphorus content of the nickel-phosphorus alloy plating, and further, the spot welding strength of the battery case is reduced.
This deterioration in spot weldability is caused by the fact that the nickel-phosphorus plating layer, which has a low melting point, melts at the contact portion with the welding tip when the temperature rises during welding, and the welding additional current density decreases, which hinders the formation of a sufficient welding nugget. It is caused by
【０００５】また熱拡散処理材の他の問題点として、ア
ルカリマンガン電池の電池性能（特に内部抵抗）が、熱
拡散処理しない材料に比較して内部抵抗がやや高いこと
が上げられる。この高内部抵抗の理由は、熱拡散処理す
るとニッケルめっき層の展延性が向上し、プレス成形加
工時に電池ケース内面に発生するクラック数が少なくな
るため、正極合剤との密着性がやや低下することが原因
である。Another problem with the heat diffusion treatment material is that the battery performance (particularly, the internal resistance) of the alkaline manganese battery is slightly higher than that of the material not subjected to the heat diffusion treatment. The reason for this high internal resistance is that the heat diffusion treatment improves the extensibility of the nickel plating layer and reduces the number of cracks generated on the inner surface of the battery case during press forming, so that the adhesion with the positive electrode mixture is slightly reduced. That is the cause.
【０００６】[0006]
【課題を解決するための手段】そこで上記問題点を解決
するため、本発明のアルカリ電池ケース用表面処理鋼板
は、鋼板を基板として、ケース外面相当側にめっき付着
量１０〜４５ｇ／ｍ2のニッケルめっき層、その上に錫
ーニッケル合金層が形成されていることを特徴とする。
また、鋼板を基板として、ケース内面相当側にめっき付
着量５〜３５ｇ／ｍ2のニッケルめっき層が形成されて
おり、ケース外面相当側にめっき付着量１０〜４５ｇ／
ｍ2 のニッケルめっき層、その上に錫ーニッケル合金層
が形成されていることが望ましい。そして、鋼板を基板
として、ケース内面相当側にめっき付着量５〜３５ｇ／
ｍ2 のニッケルめっき層、その上に錫ーニッケル合金
層が形成されており、ケース外面相当側にめっき付着量
１０〜４５ｇ／ｍ2 のニッケルめっき層、その上に錫ー
ニッケル合金層が形成されていることが望ましい。上記
表面処理鋼板は、前記ニッケルめっき層の一部又は全て
が熱処理によって鋼板中に拡散した鉄ーニッケル拡散層
が形成され、前記鉄ーニッケル拡散層の厚みが、０．２
〜６μｍであることが好ましい。さらに、本発明の電池
ケースは上記表面処理鋼板を用いたものが好ましく、本
発明の電池は上記電池ケースを用いたものが好ましい。In order to solve the above-mentioned problems, a surface-treated steel sheet for an alkaline battery case according to the present invention uses a steel sheet as a substrate and has a coating weight of 10 to 45 g / m 2 on the side corresponding to the outer surface of the case. It is characterized in that a nickel plating layer and a tin-nickel alloy layer are formed thereon.
Using a steel plate as a substrate, a nickel plating layer having a plating adhesion amount of 5 to 35 g / m 2 is formed on the inner surface side of the case, and a plating adhesion amount of 10 to 45 g / m 2 on the outer surface side of the case.
It is desirable that an m 2 nickel plating layer and a tin-nickel alloy layer be formed thereon. Then, using a steel plate as a substrate, a plating adhesion amount of 5 to 35 g /
m 2 nickel plating layer, a tin-nickel alloy layer is formed thereon, and a nickel plating layer having a plating adhesion amount of 10 to 45 g / m 2 on the side corresponding to the outer surface of the case, and a tin-nickel alloy layer is formed thereon. Is desirable. The surface-treated steel sheet is a part or all of the nickel plating layer.
Iron-nickel diffusion layer diffused into steel sheet by heat treatment
Is formed, and the thickness of the iron-nickel diffusion layer is 0.2
It is preferably about 6 μm. Further, the battery case of the present invention preferably uses the above-mentioned surface-treated steel sheet, and the battery of the present invention preferably uses the above-mentioned battery case.
【０００６】[0006]
【作用】本発明の電池ケースの外面には、ニッケルめっ
き層上に形成された硬質の錫ーニッケル合金層が存在す
るので、耐食性を損なうことなくさらに安価に耐疵付き
性をも向上させることができる。また、熱処理により軟
質の靱性を有するニッケルめっき層が存在するので、電
池ケースの被加工部（側壁部）やコーナー部、さらには
ピップ型アルカリ電池のコーナー部の耐食性が向上す
る。一方電池ケースの内面には、錫ーニッケル合金層が
形成されているので、内部抵抗や短絡電流の優れた電池
が得られる。Since the hard tin-nickel alloy layer formed on the nickel plating layer exists on the outer surface of the battery case of the present invention, it is possible to improve the scratch resistance at a lower cost without deteriorating the corrosion resistance. it can. Further, since the nickel plating layer having soft toughness is present by the heat treatment, the corrosion resistance of the processed portion (side wall portion) and the corner portion of the battery case, and the corner portion of the pip-type alkaline battery is improved. On the other hand, since the tin-nickel alloy layer is formed on the inner surface of the battery case, a battery having excellent internal resistance and short-circuit current can be obtained.
【０００７】[0007]
【実施例】以下に、本発明のアルカリ電池ケース用表面
処理鋼板、アルカリ電池ケースおよびアルカリ電池につ
いて詳細に説明する。本発明の表面処理鋼板の製造工程
は、冷延鋼板→ニッケルめっき→錫めっき→熱処理から
なり、さらに場合によっては表面粗さ調整と鋼素地の機
械的性質調整（主に腰し折れ防止）のため調質圧延が行
われる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The surface-treated steel sheet for an alkaline battery case, the alkaline battery case and the alkaline battery of the present invention will be described in detail below. The manufacturing process of the surface-treated steel sheet of the present invention comprises cold-rolled steel sheet → nickel plating → tin plating → heat treatment, and in some cases, adjustment of surface roughness and adjustment of mechanical properties of the steel base (mainly to prevent buckling and breaking). Therefore, temper rolling is performed.
【０００８】鋼板 本発明で用いる鋼板は通常、普通鋼冷延鋼板で、一般に
低炭素アルミキルド連続鋳造鋼をベースとした冷延鋼板
が主として用いられる。またＣ：０．００９重量％以下
の極低炭素鋼、さらにこれにＮｂ、Ｔｉなど遅、非時効
性元素を添加した冷延鋼板も好適に用いられる。Steel Sheet The steel sheet used in the present invention is generally a cold-rolled steel sheet of ordinary steel, and generally a cold-rolled steel sheet based on a low carbon aluminum killed continuous cast steel. C: 0.009% by weight or less of ultra-low carbon steel, and a cold-rolled steel sheet to which a slow or non-aging element such as Nb or Ti is added.
【０００９】ニッケルめっき ニッケルめっきの浴としては、ワット浴を始めとするス
ルファミン酸浴ホウフッ化物浴や塩化物浴など、工業的
に製造できるいずれのニッケルめっき浴であってもよ
い。ニッケルめっきの前処理として、通常のアルカリ脱
脂、有機溶剤脱脂、酸洗（硫酸、塩酸液中の浸漬または
電解）後水洗が施される。尚ニッケルめっきの種類とし
て、有機物を添加しない無光沢めっき、ブチンジオール
などニッケルめっき析出面を平滑化させるレベリング剤
と称する有機添加物を含有させた半光沢めっき、さらに
はナフタレンスルフォン酸塩など硫黄含有有機添加物を
含有させた鏡面光沢を呈する光沢めっき、などがある
が、本発明では、無光沢または半光沢めっきが好適に用
いられる。光沢めっきが不適の理由は、硫黄含有添加物
が電解析出中においてニッケルめっき層に混入あるいは
吸着し、後述するニッケルめっき後の熱処理においてニ
ッケルめっき層の脆化を生じ、耐食性を損なう恐れがあ
るからである。Nickel Plating The nickel plating bath may be any nickel plating bath that can be industrially produced, such as a watt bath, a sulfamic acid bath, a borofluoride bath, or a chloride bath. As a pretreatment for nickel plating, usual alkali degreasing, organic solvent degreasing, pickling (immersion in a sulfuric acid or hydrochloric acid solution or electrolysis), and then water washing are performed. The types of nickel plating include matte plating without addition of organic substances, semi-gloss plating containing an organic additive called a leveling agent that smoothes the nickel plating deposition surface such as butynediol, and sulfur-containing substances such as naphthalene sulfonate. There is a bright plating exhibiting a mirror gloss containing an organic additive, and in the present invention, a matte or semi-glossy plating is preferably used. The reason why bright plating is unsuitable is that the sulfur-containing additive may be mixed or adsorbed into the nickel plating layer during electrolytic deposition, causing embrittlement of the nickel plating layer in a heat treatment after nickel plating described below, which may impair corrosion resistance. Because.
【００１０】ケース外面相当側に施されているニッケル
付着量の下限は１０ｇ／ｍ2 であり、上限は４５ｇ／ｍ
2 である。望ましくは下限は１５ｇ／ｍ2 、上限は３５
ｇ／ｍ2 、さらに望ましくは下限は２０ｇ／ｍ2 、上限
は３０ｇ／ｍ2 が好適である。付着量が１０ｇ／ｍ2 未
満の場合は鋼板の表面にニッケルが充分にめっきされず
に耐食性付与に十分でなく、一方４５ｇ／ｍ2 を越える
と本発明効果が飽和してしまい、不経済であるとともに
製品の価格競争力を失うからである。一方、ケース内面
相当側に施されているニッケル付着量の下限は５ｇ／ｍ
2 であり、上限は３５ｇ／ｍ2 である。望ましくは下限
が８ｇ／ｍ2 、上限は２５ｇ／ｍ2 、さらに望ましくは
下限が１０ｇ／ｍ2 、上限は２０ｇ／ｍ2 が好適に採用
される。付着量が５ｇ／ｍ2 未満の場合は鋼板の表面に
ニッケルが充分にめっきされず、一方３５ｇ／ｍ2 を越
えると本発明効果が飽和してしまい、不経済であるとと
もに製品の価格競争力を失うからである。The lower limit of the amount of nickel deposited on the side corresponding to the outer surface of the case is 10 g / m 2 , and the upper limit is 45 g / m 2.
2 Preferably, the lower limit is 15 g / m 2 and the upper limit is 35.
g / m 2 , more preferably, the lower limit is 20 g / m 2 , and the upper limit is 30 g / m 2 . When the amount is less than 10 g / m 2 , nickel is not sufficiently plated on the surface of the steel sheet to provide sufficient corrosion resistance. On the other hand, when the amount exceeds 45 g / m 2 , the effect of the present invention is saturated, which is uneconomical. At the same time, the price competitiveness of the product is lost. On the other hand, the lower limit of the amount of nickel attached to the inner surface of the case is 5 g / m2.
2 , and the upper limit is 35 g / m 2 . Preferably, the lower limit is 8 g / m 2 , the upper limit is 25 g / m 2 , and the lower limit is 10 g / m 2 and the upper limit is 20 g / m 2 . If the adhesion amount is less than 5 g / m 2 , nickel is not sufficiently plated on the surface of the steel sheet, while if it exceeds 35 g / m 2 , the effect of the present invention is saturated, which is uneconomical and price competitiveness of the product. Because it loses.
【００１１】錫めっき 錫めっきは上記ニッケルめっき層の上に析出され、その
後の熱処理によって錫ーニッケル合金層となる。錫めっ
きを鋼板の片面にのみ施す場合はケース外面相当面側に
施し、その付着量の下限は０．５ｇ／ｍ2 であり、上限
は１０ｇ／ｍ2 である。望ましくは下限が１ｇ／ｍ2 、
上限は８ｇ／ｍ2 、さらに望ましくは下限が１．５ｇ／
ｍ2 、上限は７ｇ／ｍ2 が好適に採用される。下限が
０．５ｇ／ｍ2 未満の場合は、熱処理によって形成され
る錫ーニッケル合金層の硬度が低いので耐疵付き性効果
が薄く、１０ｇ／ｍ2 を越えると本発明の効果が飽和に
達し、不経済であることによる。Tin Plating Tin plating is deposited on the nickel plating layer, and becomes a tin-nickel alloy layer by a subsequent heat treatment. When tin plating is applied to only one surface of the steel sheet, it is applied to the surface corresponding to the outer surface of the case, and the lower limit of the amount of adhesion is 0.5 g / m 2 and the upper limit is 10 g / m 2 . Desirably, the lower limit is 1 g / m 2 ,
The upper limit is 8 g / m 2 , and more preferably the lower limit is 1.5 g / m 2 .
m 2 , and the upper limit is preferably 7 g / m 2 . When the lower limit is less than 0.5 g / m 2 , the tin-nickel alloy layer formed by the heat treatment has a low hardness, so that the effect of scratch resistance is small, and when it exceeds 10 g / m 2 , the effect of the present invention reaches saturation. , Because it is uneconomical.
【００１２】ケース内面相当面側にも錫めっきを施す場
合（両面に錫めっきを施すこととなる）には、錫めっき
付着量の下限は１ｇ／ｍ2 であり、上限は１０ｇ／ｍ2
である。望ましくは、下限が２ｇ／ｍ2 であり、上限は
９ｇ／ｍ2 である。さらに望ましくは、下限が３ｇ／ｍ
2 であり、上限は８ｇ／ｍ2 である。下限が１ｇ／ｍ2
未満の場合内部抵抗値を低下させる効果が充分でなく、
上限が１０ｇ／ｍ2 を越える場合は、熱処理で形成され
る錫ーニッケル合金による電池性能の効果が飽和に達し
不経済である。When tin plating is also applied to the side corresponding to the inner surface of the case (tin plating is applied to both sides), the lower limit of the amount of tin plating is 1 g / m 2 and the upper limit is 10 g / m 2.
It is. Desirably, the lower limit is 2 g / m 2 and the upper limit is 9 g / m 2 . More preferably, the lower limit is 3 g / m.
2 , and the upper limit is 8 g / m 2 . Lower limit is 1 g / m 2
If less than the effect of lowering the internal resistance is not sufficient,
When the upper limit exceeds 10 g / m 2 , the effect of the battery performance by the tin-nickel alloy formed by the heat treatment reaches saturation and is uneconomical.
【００１３】錫めっきの方法は、脱脂、酸洗、錫めっ
き、リフロー（錫溶融処理）、ケミカル処理の工程で製
造される場合が一般的であるが、本発明においては、錫
めっき層の酸化による黄変防止、塗装密着性向上のため
施されるケミカル処理（クロム酸または重クロム酸塩液
中への浸漬または電解処理）は行わない。その理由はク
ロム元素は電気接触抵抗値が高くなり電池性能上好まし
くないからである。錫めっき液は通常工業的に使用され
る酸性浴、アルカリ浴のいずれでも良く、硫酸第一錫浴
やフェノールスルフォン酸浴が好適に用いられる。The method of tin plating is generally performed in the steps of degreasing, pickling, tin plating, reflow (tin melting treatment), and chemical treatment. In the present invention, however, the tin plating layer is oxidized. No chemical treatment (immersion in a chromic acid or dichromate solution or electrolytic treatment) for preventing yellowing and improving the adhesion of the coating due to the above. The reason is that the chromium element increases the electric contact resistance and is not preferable in battery performance. The tin plating solution may be any of an acidic bath and an alkali bath which are usually used industrially, and a stannous sulfate bath or a phenolsulfonic acid bath is preferably used.
【００１４】熱処理 本発明においては、ニッケルめっきに引き続き、片面若
しくは両面に上記錫めっきを施した後熱処理を行う。熱
処理を行う理由は、 （１）鋼素地上に形成させたニッケルめっき層の一部を
鋼板中に拡散させ、一部を靱性のあるニッケルめっき層
にする。あるいはニッケルめっき層を全て鉄ーニッケル
拡散層にする。 （２）ニッケルめっき層上に形成した錫めっき層を、錫
ーニッケル合金層にする。 本発明は、上記（１）、（２）の２つの目的を熱処理に
よって同時に得んとするものであり、より経済的に製造
できる。上記（１）は、実用的には熱処理温度４５０℃
において鉄ーニッケル拡散層が形成される。４５０℃以
下でも長時間の熱処理で拡散層は形成されるが、その厚
さは微小である。また熱処理温度４５０℃以上で、ニッ
ケルめっき層中の樹脂状析出組織が再結晶し、ニッケル
めっき層はめっき歪み（引張り応力）が解放され軟質化
する。また、同時に鋼素地との界面でニッケルと鉄が相
互に拡散し始める。拡散層の厚さは熱処理の温度と時間
により決定される。温度が高く且つ処理時間が長く、さ
らにニッケルめっき厚が薄い場合には、ニッケルめっき
層は全て鉄ーニッケル拡散層となる。Heat Treatment In the present invention, after the nickel plating, one side or both sides are subjected to the tin plating and then heat treated. The reasons for performing the heat treatment are as follows: (1) A part of the nickel plating layer formed on the steel substrate is diffused into the steel sheet, and a part of the nickel plating layer is formed into a tough nickel plating layer. Alternatively, the entire nickel plating layer is an iron-nickel diffusion layer. (2) The tin plating layer formed on the nickel plating layer is changed to a tin-nickel alloy layer. In the present invention, the two objects (1) and (2) are simultaneously obtained by heat treatment, and the production can be performed more economically. The above (1) is practically a heat treatment temperature of 450 ° C.
In this, an iron-nickel diffusion layer is formed. Even at 450 ° C. or lower, a diffusion layer is formed by a long-time heat treatment, but its thickness is minute. Further, at a heat treatment temperature of 450 ° C. or more, the resinous precipitation structure in the nickel plating layer is recrystallized, and the plating distortion (tensile stress) of the nickel plating layer is released and the nickel plating layer is softened. At the same time, nickel and iron begin to diffuse into each other at the interface with the steel substrate. The thickness of the diffusion layer is determined by the temperature and time of the heat treatment. When the temperature is high, the processing time is long, and the nickel plating thickness is small, the entire nickel plating layer becomes an iron-nickel diffusion layer.
【００１５】上記の熱処理で生成される鉄ーニッケル拡
散層については、その厚さの下限は０．２μｍが望まし
く、上限は６μｍが好適である。望ましくは下限が０．
５μｍ、上限は５μｍ、さらに望ましくは下限が１μ
ｍ、上限は４μｍが好適に採用される。The lower limit of the thickness of the iron-nickel diffusion layer formed by the above heat treatment is preferably 0.2 μm, and the upper limit is preferably 6 μm. Preferably, the lower limit is 0.
5 μm, upper limit is 5 μm, more preferably lower limit is 1 μm
m, the upper limit is preferably 4 μm.
【００１６】付着量が０．２μｍ未満の場合は鉄ーニッ
ケル拡散層の生成厚みが少なくて十分なめっき付着性を
確保できず、一方６μｍを越える処理は本発明効果が飽
和してしまうとともに、熱拡散処理に高温または長時間
を要し不経済であり製品の価格競争力を失うからであ
る。この熱処理において、上記鉄ーニッケル拡散層の形
成と同時に、ニッケルめっき層上に形成されている錫め
っき層が、錫ーニッケル合金層となる。錫ーニッケル合
金層は、比較的低温（１８０℃程度）で形成される。こ
の合金化によって生成される金属間化合物としては、Ｎ
ｉ3 Ｓｎ、Ｎｉ3 Ｓｎ2 、Ｎｉ3 Ｓｎ4 があり、この存
在の確認はＸ線回折分析法によって行うことができる。
これらの金属間化合物の生成により錫ーニッケル合金層
は、硬くてしかも耐アルカリ腐食性を有し、さらに電気
接触抵抗が低く且つ安定であるという、電池用材料とし
て極めて優れた特性を持つ。If the amount of adhesion is less than 0.2 μm, the thickness of the formed iron-nickel diffusion layer is too small to ensure sufficient plating adhesion. On the other hand, the treatment exceeding 6 μm saturates the effect of the present invention, This is because the diffusion process requires a high temperature or a long time, is uneconomical, and loses price competitiveness of the product. In this heat treatment, at the same time as the formation of the iron-nickel diffusion layer, the tin plating layer formed on the nickel plating layer becomes a tin-nickel alloy layer. The tin-nickel alloy layer is formed at a relatively low temperature (about 180 ° C.). As the intermetallic compound generated by this alloying, N
There are i3Sn, Ni3Sn2, and Ni3Sn4, the presence of which can be confirmed by X-ray diffraction analysis.
Due to the formation of these intermetallic compounds, the tin-nickel alloy layer has extremely excellent properties as a battery material, such as being hard, having alkali corrosion resistance, and having low and stable electric contact resistance.
【００１７】本発明者らは、熱処理によって形成された
錫ーニッケル合金層が電池ケースとして極めて好適であ
ることを次のような実験で確かめた。即ち、板厚が０．
２５ｍｍの冷延鋼板に２μｍ厚のニッケルめっきを施
し、温度４００℃、時間１時間の非酸化性ガス雰囲気内
で熱処理した試料Ａと、該ニッケルめっきに引き続き１
１ｇ／ｍ2 の錫めっきを行った後熱処理した試料Ｂとを
作成した。試料Ａと試料Ｂの表面硬度（ビッカース硬
度，荷重１０ｇ）を測定した結果、Ａ試料は値１９５を
示すのに対し、錫ーニッケル合金化したＢ試料は値８０
５と著しく硬化している。さらに試料Ａ，Ｂを用いて外
径１３ｍｍ、高さ４９ｍｍの有底円筒ケース（電池ケー
ス）に深絞り成形し、該ケースの１／２高さ程の位置の
内面を電子顕微鏡で観察した。試料Ａは表面が滑らかで
あるのに対し、錫ーニッケル合金化して硬質化した試料
Ｂはマイクロクラックが多数見られる。このマイクロク
ラックには、アルカリ電池の正極合剤が入り込む結果電
池ケース内面との密着力が向上し、電池内部抵抗は低減
するものと思われる。この結果から、試料Ｂが電池ケー
ス用材料として好適である。The present inventors have confirmed by the following experiments that the tin-nickel alloy layer formed by the heat treatment is extremely suitable as a battery case. That is, the plate thickness is 0.
A sample A was prepared by applying a 2 μm-thick nickel plating to a 25-mm cold-rolled steel sheet and heat-treating it at 400 ° C. for 1 hour in a non-oxidizing gas atmosphere.
Sample B, which was subjected to a tin plating of 1 g / m 2 and then heat-treated, was prepared. As a result of measuring the surface hardness (Vickers hardness, load 10 g) of Sample A and Sample B, Sample A showed a value of 195, while Sample B, which had been tin-nickel alloyed, had a value of 80.
5 and remarkably hardened. Further, the samples A and B were deep drawn into a bottomed cylindrical case (battery case) having an outer diameter of 13 mm and a height of 49 mm, and the inner surface at a position about half the height of the case was observed with an electron microscope. Sample A has a smooth surface, whereas Sample B, which is hardened by a tin-nickel alloy, has many microcracks. It is considered that as a result of the positive electrode mixture of the alkaline battery entering the microcrack, the adhesion to the inner surface of the battery case is improved, and the internal resistance of the battery is reduced. From this result, Sample B is suitable as a battery case material.
【００１８】ところで、工業的な熱処理の方法には箱型
焼鈍法と連続焼鈍法の方法があるが、本発明ではいずれ
の方法も採用される。箱型焼鈍法は６５０℃程度以下で
数時間以上の長時間熱処理時間であるのに対し、連続焼
鈍法の場合は、６００℃程度〜８５０℃程度の比較的高
温で、時間は数分以下の短時間熱処理である。By the way, industrial heat treatment methods include a box annealing method and a continuous annealing method, and in the present invention, both methods are adopted. The box annealing method has a long heat treatment time of several hours or more at about 650 ° C. or less, whereas the continuous annealing method has a relatively high temperature of about 600 ° C. to 850 ° C. and the time is several minutes or less. This is a short-time heat treatment.
【００１９】調質圧延 さらに熱処理後、表面に所望の表面粗さを付与し、熱処
理によって生じる腰折れを防止するため、調質圧延する
方法も本発明において好適に用いられる。通常砥石研摩
したブライト仕上げと称し、圧下率１〜３％程度の調質
圧延を行う。ブライト仕上げの他、ショットブラスト研
摩したワークロールで調質圧延を行ったダル仕上げを用
いてもよい。Temper rolling Further, after the heat treatment, a method of temper rolling is preferably used in the present invention in order to impart a desired surface roughness to the surface and prevent buckling caused by the heat treatment. It is usually called "bright finishing" in which a stone is polished, and temper rolling at a rolling reduction of about 1 to 3% is performed. In addition to the bright finish, a dull finish subjected to temper rolling with a work roll subjected to shot blast polishing may be used.
【００２０】電池ケース作成 上記の表面処理鋼板を用いて、深絞り、ＤＩ（ｄｒａｗ
ａｎｄ ｉｒｏｎｉｎｇ）、ＤＴＲ（ｄｒａｗ ｔｈ
ｉｎ ａｎｄ ｒｅｄｒａｗ）等の公知の成形法によっ
て電池ケースを製造する。表面処理鋼板の表裏には異な
った種類の被覆が施されているので、電池ケースの作成
にあたっては、表面処理鋼板のいずれの側が成形後に電
池ケースの内あるいは外側になるかに留意して成形す
る。Preparation of Battery Case Using the above surface-treated steel sheet, deep drawing, DI (draw)
and ironing), DTR (draw th
The battery case is manufactured by a known molding method such as in and redraw. Since different types of coatings are applied to the front and back of the surface-treated steel sheet, when forming the battery case, shape the surface-treated steel sheet taking into account which side of the surface-treated steel sheet will be inside or outside the battery case after forming .
【００２１】[0021]
【実施例】以下に実施例によって、本発明をさらに詳細
に説明する。 （実施例１）板厚０．２５ｍｍの冷延、焼鈍済みの低炭
素アルミキルド鋼板をめっき原板とした。鋼化学組成は
下記の通りである。Ｃ：０．０３％（％は重量％、以下
同じ）、Ｍｎ：０．１８％、Ｓｉ：０．０１％、Ｐ：
０．０１３％、Ｓ：０．０１２％、Ａｌ：０．０５４
％、Ｎ：０．００３８％。上記鋼板を、アルカリ電解脱
脂（苛性ソーダ３０ｇ／ｌ、５Ａ／ｄｍ2 （陽極処理）
×１０秒、５Ａ／ｄｍ2 （陰極処理）×１０秒、浴温７
０℃）、硫酸酸洗（硫酸５０ｇ／ｌ、浴温３０℃、２０
秒浸漬）を行った後、下記の条件でニッケルめっきを行
った。 浴組成；硫酸ニッケル ３２０ｇ／ｌ 塩化ニッケル ４０ｇ／ｌ ほう酸 ３０ｇ／ｌ 市販品半光沢剤 １ｇ／ｌ （不飽和アルコールポリオキシエチレン、不飽和カルボン酸含有） ラウリル硫酸ソーダ ０．５ｇ／ｌ 浴温度； ５５±２℃ ｐＨ ； ４．１〜４．６ 攪拌 ； 空気攪拌 電流密度； １５Ａ／ｄｍ2 アノード； ニッケルペレット（チタンバスケットにニッケルペレット充填、 ポリプロピレン製バッグでチタンバスケットを覆う） 上記の条件で、両面に半光沢ニッケルめっきを行い、そ
の厚みを上記条件で電解時間を変化させて、ニッケルめ
っきの厚みを変化させた。ニッケルめっき後、熱処理す
る方法は、水素６．５％、残部窒素ガス、露点ー４０℃
の保護ガスを用いて、熱処理を行った。ニッケルめっき
に引き続き、硫酸第一錫めっき浴で錫めっきを行った。 浴組成； 硫酸第一錫 ３０ｇ／ｌ（Ｓ++） フェノールスルフォン酸 ６０ｇ／ｌ エトキシ化αナフトール ５ｇ／ｌ 浴温度； ５０±２℃ 電流密度；２０Ａ／ｄｍ2 アノード；錫板 付着量（めっき厚み）は電解時間を変えて変化させた。
錫めっき後、熱処理する方法は、水素６．５％、残部窒
素ガス、露点ー４０℃の保護ガスを用いて、均熱温度、
均熱時間を変化させて熱処理を行った。さらに錫めっき
後に、ブライト砥石仕上げのワークロールで、伸び率
１．３％の調質圧延を行った。製造条件を異ならしめ
て、本発明の表面処理鋼板の実施例１〜１０と、比較例
１１〜１５を作成した。この一覧表を表１に示す。The present invention will be described in more detail with reference to the following examples. (Example 1) A cold rolled and annealed low carbon aluminum killed steel sheet having a sheet thickness of 0.25 mm was used as a plating base sheet. The steel chemical composition is as follows. C: 0.03% (% is% by weight, the same applies hereinafter), Mn: 0.18%, Si: 0.01%, P:
0.013%, S: 0.012%, Al: 0.054
%, N: 0.0038%. The above steel sheet is subjected to alkaline electrolytic degreasing (caustic soda 30 g / l, 5 A / dm 2 (anodizing))
× 10 seconds, 5 A / dm 2 (cathode treatment) × 10 seconds, bath temperature 7
0 ° C), sulfuric acid washing (sulfuric acid 50 g / l, bath temperature 30 ° C, 20
Immersion for 2 seconds), and then nickel plating was performed under the following conditions. Bath composition: Nickel sulfate 320 g / l Nickel chloride 40 g / l Boric acid 30 g / l Commercially available semi-brightener 1 g / l (containing unsaturated alcohol polyoxyethylene and unsaturated carboxylic acid) Sodium lauryl sulfate 0.5 g / l Bath temperature; 55 ± 2 ° C. pH; 4.1-4.6 Stirring; Air stirring Current density; 15 A / dm 2 anode; Nickel pellets (filled with titanium pellets in titanium basket, cover titanium basket with polypropylene bag) Semi-bright nickel plating was performed on both surfaces, and the thickness of the nickel plating was changed by changing the electrolysis time under the above conditions. After nickel plating, the heat treatment method is 6.5% hydrogen, the balance is nitrogen gas, and the dew point is -40 ° C.
The heat treatment was performed using the protective gas described above. Subsequent to nickel plating, tin plating was performed in a stannous sulfate plating bath. Bath composition; stannous sulfate 30 g / l (S ++) phenolsulfonic acid 60 g / l ethoxylated α-naphthol 5 g / l bath temperature; 50 ± 2 ° C. current density; 20 A / dm 2 anode; tin plate Thickness) was changed by changing the electrolysis time.
After the tin plating, the heat treatment is performed by using a 6.5% hydrogen gas, a residual nitrogen gas, and a protective gas having a dew point of −40 ° C., soaking temperature,
The heat treatment was performed while changing the soaking time. Further, after tin plating, temper rolling at an elongation of 1.3% was performed with a work roll finished with a bright grindstone. The manufacturing conditions were changed, and Examples 1 to 10 of the surface-treated steel sheet of the present invention and Comparative Examples 11 to 15 were prepared. Table 1 shows this list.
【００２２】[0022]
【表１】 さらに上記実施例および比較例の試料を用いて、筒型ア
ルカリ電池で使用される標準タイプのＪＩＳーＬＲ６型
（単３型）の正極缶（電池ケース）を作製した。また、
そのケースを用いて電池を作成した。まず、表面処理鋼
板を円盤状に打ち抜いたブランクを作成し、深絞り成形
法を用い１０工程で、ケース長さ４９．３ｍｍ，ケース
外径１３．８ｍｍの有底筒型電池ケース（ＬＲ６型）を
作成した。次に、電解二酸化マンガンとグラファイトを
混練器に投入し、水酸化カリウムを添加しながら混合し
て正極合剤を作成した。次いで上記深絞り成形加工によ
り作成したＬＲ６型電池ケースに正極合剤を挿入した。
次いでビニロン系不織布からなるセパレーターを上記電
池ケースに挿入した後、所定量の水酸化カリウムを滴下
した。上記のようにして設置したセパレータの有底筒内
に、粒状亜鉛、水酸化カリウム液および増粘剤からなる
ゲル状負極合剤を所定量注入した。さらに電池ケースの
開口部を、真鍮棒を溶接した負極端子によって閉蓋しア
ルカリ電池を作製した。閉蓋にあたってはポリアミド樹
脂製の絶縁ガスケットを装着した。以上のように作成し
た表面処理鋼板および電池について、下記の方法で評価
試験を行った。[Table 1] Further, a standard type JIS-LR6 type (AA type) positive electrode can (battery case) used in a cylindrical alkaline battery was prepared using the samples of the above-described Examples and Comparative Examples. Also,
A battery was made using the case. First, a blank was prepared by punching a surface-treated steel sheet into a disc shape, and a deep-drawing forming method was used to form a bottomed cylindrical battery case (LR6 type) having a case length of 49.3 mm and a case outer diameter of 13.8 mm in 10 steps. It was created. Next, electrolytic manganese dioxide and graphite were charged into a kneader, and mixed while adding potassium hydroxide to prepare a positive electrode mixture. Next, the positive electrode mixture was inserted into the LR6 type battery case prepared by the deep drawing process.
Next, after inserting a separator made of a vinylon-based nonwoven fabric into the battery case, a predetermined amount of potassium hydroxide was dropped. A predetermined amount of a gelled negative electrode mixture comprising granular zinc, a potassium hydroxide solution and a thickener was injected into the bottomed cylinder of the separator set as described above. Further, the opening of the battery case was closed with a negative electrode terminal to which a brass rod was welded, thereby producing an alkaline battery. Upon closing, an insulating gasket made of polyamide resin was attached. An evaluation test was performed on the surface-treated steel sheet and the battery prepared as described above by the following method.
【００２３】（評価試験法） （１）硬度測定 めっき表層の硬度測定はマイクロビッカース硬度計を用
い、荷重１０ｇで測定した。測定数を３としてその平均
値を硬度とした。 （２）耐疵付き性評価 めっき表層の耐疵付き性評価は、引掻強度試験機（新東
科学（株）製ＨＥＩＤＯＮー１４Ｓ／Ｄ）を用い、一定
荷重の下で試料をサファイア針で引っ掻いた。その際の
試料表面の疵付き状態を観察し、疵が観察され始める荷
重（ｇ）で評価した。測定数を３とし、疵付きが観察さ
れる最も軽い荷重を採用した。 （３）電池性能評価 作製したアルカリ電池ＬＲ６型の電池性能評価は次のよ
うにした。即ち、６０℃で１ケ月間恒温層に貯蔵し、交
流インピーダンス法（周波数１ｋＨｚ）による内部抵抗
値（ｍΩ）並びに短絡電流（抵抗１ｍΩ）を測定した。
評価は、両試験とも１０試料を測定して平均値を採用し
た。上記評価の結果を表２に示す。(Evaluation Test Method) (1) Measurement of Hardness The hardness of the plating surface layer was measured with a micro Vickers hardness meter under a load of 10 g. With the number of measurements taken as 3, the average value was taken as hardness. (2) Evaluation of scratch resistance The evaluation of the scratch resistance of the plating surface layer was performed using a scratch strength tester (HEIDON-14S / D manufactured by Shinto Kagaku Co., Ltd.) and the sample was sapphire under a constant load. I was scratched. At that time, the state of scratches on the surface of the sample was observed, and evaluation was made based on a load (g) at which scratches were observed. The number of measurements was set to 3, and the lightest load at which flaws were observed was adopted. (3) Battery Performance Evaluation The battery performance of the prepared alkaline battery LR6 was evaluated as follows. That is, it was stored in a thermostat at 60 ° C. for one month, and the internal resistance value (mΩ) and the short-circuit current (resistance 1 mΩ) were measured by the AC impedance method (frequency 1 kHz).
For the evaluation, an average value was adopted by measuring 10 samples in both tests. Table 2 shows the results of the evaluation.
【００２４】[0024]
【表２】 表２において本発明の実施例である試料はいずれも、硬
度、耐疵付き性および電池性能において比較例よりも優
れた結果が得られた。電池内部抵抗が下がる理由は、電
池ケース成形加工時、硬質の錫ーニッケル合金層中にマ
イクロクラックが生ずるため、正極合剤との密着性が高
くなり、接触抵抗が下がるからである。[Table 2] In Table 2, all of the samples according to the examples of the present invention showed superior results in hardness, scratch resistance, and battery performance as compared with the comparative example. The reason why the internal resistance of the battery is reduced is that micro-cracks are generated in the hard tin-nickel alloy layer at the time of forming the battery case, so that the adhesion to the positive electrode mixture increases and the contact resistance decreases.
【００２５】[0025]
【発明の効果】本発明の表面処理鋼板は、電池ケースの
外面に、ニッケルめっき層上に形成された硬質の錫ーニ
ッケル合金層が存在するよう構成されているので、耐食
性を損なうことなくさらに安価に耐疵付き性を向上させ
た電池ケースを提供することができる。また、本発明の
表面処理鋼板は、電池ケースの内面に、錫ーニッケル合
金層が形成されるよう構成されているので、内部抵抗や
短絡電流の優れた電池を提供できる。The surface-treated steel sheet of the present invention is configured so that the hard tin-nickel alloy layer formed on the nickel plating layer is present on the outer surface of the battery case, so that the cost is reduced without deteriorating the corrosion resistance. And a battery case with improved scratch resistance. Further, since the surface-treated steel sheet of the present invention is configured such that the tin-nickel alloy layer is formed on the inner surface of the battery case, a battery having excellent internal resistance and short-circuit current can be provided.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 井内 秀典 山口県下松市東豊井1302番地 東洋鋼鈑 株式会社下松工場内 (72)発明者 池高 聖 山口県下松市東豊井1302番地 東洋鋼鈑 株式会社下松工場内 (56)参考文献 特開 平６−108286（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C25D 1/00 - 7/12 H01M 2/02 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hidenori Inuchi 1302 Higashitoyoi, Kudamatsu City, Yamaguchi Prefecture Toyo Kohan Co., Ltd.Kudamatsu Plant (56) References JP-A-6-108286 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C25D 1/00-7/12 H01M 2/02
Claims (6)
めっき付着量１０〜４５ｇ／ｍ2 のニッケルめっき層、
その上に錫ーニッケル合金層が形成されているアルカリ
電池ケース用表面処理鋼板。1. A nickel-plated layer having a coating weight of 10 to 45 g / m 2 on a side corresponding to an outer surface of a case using a steel plate as a substrate,
A surface-treated steel sheet for an alkaline battery case, on which a tin-nickel alloy layer is formed.
めっき付着量５〜３５ｇ／ｍ2 のニッケルめっき層が形
成されており、ケース外面相当側にめっき付着量１０〜
４５ｇ／ｍ2 のニッケルめっき層、その上に錫ーニッケ
ル合金層が形成されているアルカリ電池ケース用表面処
理鋼板。2. A steel plate is used as a substrate, and a nickel plating layer having a plating weight of 5 to 35 g / m 2 is formed on a side corresponding to the inner surface of the case, and a plating weight of 10 to 35 g / m 2 on a side corresponding to the outer surface of the case.
A surface-treated steel sheet for an alkaline battery case having a nickel plating layer of 45 g / m 2 and a tin-nickel alloy layer formed thereon.
めっき付着量５〜３５ｇ／ｍ2 のニッケルめっき層、そ
の上に錫ーニッケル合金層が形成されており、ケース外
面相当側にめっき付着量１０〜４５ｇ／ｍ2 のニッケル
めっき層、その上に錫ーニッケル合金層が形成されてい
るアルカリ電池ケース用表面処理鋼板。3. A steel plate as a substrate, a nickel plating layer having a coating weight of 5 to 35 g / m 2 on a side corresponding to the inner surface of the case, and a tin-nickel alloy layer formed thereon, and a plating coating amount on a side corresponding to the outer surface of the case. A surface-treated steel sheet for an alkaline battery case having a nickel plating layer of 10 to 45 g / m 2 and a tin-nickel alloy layer formed thereon.
熱処理によって鋼板中に拡散した鉄ーニッケル拡散層が
形成され、前記鉄ーニッケル拡散層の厚みが、０．２〜
６μｍである請求項１〜３のいずれかに記載のアルカリ
電池ケース用表面処理鋼板。 4. A part or all of the nickel plating layer
The iron-nickel diffusion layer diffused into the steel sheet by heat treatment
Formed, the thickness of the iron-nickel diffusion layer is 0.2 to
The surface-treated steel sheet for an alkaline battery case according to any one of claims 1 to 3, which is 6 µm.
面処理鋼板を用いたアルカリ電池ケース。5. An alkaline battery case using the surface-treated steel sheet according to claim 1. Description:
ルカリ電池。6. An alkaline battery using the battery case according to claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11407194A JP3272866B2 (en) | 1994-04-27 | 1994-04-27 | Surface treated steel sheet for alkaline battery case, alkaline battery case and alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11407194A JP3272866B2 (en) | 1994-04-27 | 1994-04-27 | Surface treated steel sheet for alkaline battery case, alkaline battery case and alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07300695A JPH07300695A (en) | 1995-11-14 |
| JP3272866B2 true JP3272866B2 (en) | 2002-04-08 |
Family
ID=14628322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11407194A Expired - Fee Related JP3272866B2 (en) | 1994-04-27 | 1994-04-27 | Surface treated steel sheet for alkaline battery case, alkaline battery case and alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3272866B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004093220A1 (en) * | 2003-04-16 | 2004-10-28 | Toyo Kohan Co. Ltd. | Surface-treated steel for battery case and battery case |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3432523B2 (en) | 1996-09-03 | 2003-08-04 | 東洋鋼鈑株式会社 | Surface-treated steel sheet for battery case, battery case, and battery using the same |
| WO2001042537A1 (en) * | 1999-12-09 | 2001-06-14 | Toyo Kohan Co., Ltd. | Surface treated steel sheet for battery case, battery case using it, and battery using the case |
| JP3854464B2 (en) | 2001-01-09 | 2006-12-06 | 新日本製鐵株式会社 | Ni-plated steel plate for alkaline manganese battery positive electrode can |
| EP2522763A4 (en) | 2010-01-08 | 2017-03-08 | Toyo Kohan Co., Ltd. | Surface-treated metal sheet and process for producing formed article from the surface-treated metal sheet |
| JP5923272B2 (en) * | 2011-10-14 | 2016-05-24 | セイコーインスツル株式会社 | Electrochemical cell, lid and method for producing electrochemical cell |
| JP5668709B2 (en) * | 2012-02-22 | 2015-02-12 | 新日鐵住金株式会社 | Surface-treated steel sheet for lithium ion battery case with excellent press formability and manufacturing method thereof |
-
1994
- 1994-04-27 JP JP11407194A patent/JP3272866B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004093220A1 (en) * | 2003-04-16 | 2004-10-28 | Toyo Kohan Co. Ltd. | Surface-treated steel for battery case and battery case |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07300695A (en) | 1995-11-14 |
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