JP2006307321A - Plated steel sheet for battery vessel, battery vessel using the plated steel sheet for battery vessel, and battery using the battery vessel - Google Patents
Plated steel sheet for battery vessel, battery vessel using the plated steel sheet for battery vessel, and battery using the battery vessel Download PDFInfo
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- JP2006307321A JP2006307321A JP2006011700A JP2006011700A JP2006307321A JP 2006307321 A JP2006307321 A JP 2006307321A JP 2006011700 A JP2006011700 A JP 2006011700A JP 2006011700 A JP2006011700 A JP 2006011700A JP 2006307321 A JP2006307321 A JP 2006307321A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 85
- 239000010959 steel Substances 0.000 title claims abstract description 85
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 47
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- 239000004332 silver Substances 0.000 claims abstract description 29
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 26
- 239000010941 cobalt Substances 0.000 claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 3
- 238000007747 plating Methods 0.000 abstract description 83
- 238000010438 heat treatment Methods 0.000 abstract description 19
- 239000000203 mixture Substances 0.000 abstract description 14
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- 238000000137 annealing Methods 0.000 description 25
- 238000000034 method Methods 0.000 description 20
- 238000009792 diffusion process Methods 0.000 description 19
- 229910000655 Killed steel Inorganic materials 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910001096 P alloy Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000010409 ironing Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 4
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- NPURPEXKKDAKIH-UHFFFAOYSA-N iodoimino(oxo)methane Chemical compound IN=C=O NPURPEXKKDAKIH-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 2
- 239000010956 nickel silver Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical class NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YCGSKCXSSVUUKX-UHFFFAOYSA-L [I-].[K+].[Ag+].CS(=O)(=O)[O-] Chemical compound [I-].[K+].[Ag+].CS(=O)(=O)[O-] YCGSKCXSSVUUKX-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- 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
Abstract
Description
本発明は、電池容器用めっき鋼板、その電池容器用めっき鋼板を用いた電池容器およびその電池容器を用いた電池に関する。 The present invention relates to a plated steel sheet for battery containers, a battery container using the plated steel sheet for battery containers, and a battery using the battery container.
近年、デジタルカメラ、ＣＤ、ＭＤプレーヤー、液晶テレビ、ゲーム機器など携帯用ＡＶ機器や携帯電話の発展とともに、重負荷の作動電源として一次電池であるアルカリ電池、二次電池であるニッケル水素電池、リチウムイオン電池などが多用されている。これらの電池においては、高出力化および長寿命化など、高性能化が求められており、正極および負極活物質を充填する電池容器も電池の重要な構成要素としての性能の向上が求められている。例えばアルカリ乾電池の場合、長寿命化を目的として電解液であるアルカリ溶液に対する耐食性を向上させるために、電池ケースの内面となる側にニッケル−リン合金層が形成されている電池容器用表面処理鋼板（例えば特許文献１参照）が提案されている。 In recent years, along with the development of portable AV equipment and mobile phones such as digital cameras, CDs, MD players, liquid crystal televisions, game machines, etc., alkaline batteries as primary batteries, nickel-metal hydride batteries as secondary batteries, lithium as operating power sources for heavy loads Ion batteries are often used. In these batteries, there is a demand for higher performance such as higher output and longer life, and battery containers filled with positive and negative electrode active materials are also required to have improved performance as important components of the battery. Yes. For example, in the case of an alkaline battery, a surface-treated steel sheet for a battery container in which a nickel-phosphorus alloy layer is formed on the inner surface of the battery case in order to improve the corrosion resistance against an alkaline solution that is an electrolytic solution for the purpose of extending the life. (See, for example, Patent Document 1).
また、電池の高容量化、および貯蔵後の重負荷特性の劣化を防止するため、缶内面になる面の圧延鋼板材にニッケル−銀合金メッキ層、またはニッケル−クロム合金メッキ層を形成し、プレス絞りしごき加工して細かいひび割れを生じさせて凹凸面を構成し、正極合剤や導電性被膜との接触面積を大きくして電池の内部抵抗を減少させる方法（例えば特許文献２参照）や、ニッケルメッキ層を形成させ、その上に銀メッキ層を形成させた後、加熱処理してニッケル−銀メッキ層を形成させてメッキの結晶を撤密化して硬度を高め、ひび割れの間隔を一層密にすることにより、正極合剤や導電性被膜との接触面積をさらに大きくして電池の内部抵抗を減少させる電池缶（例えば特許文献３参照）が提案されている。 In addition, in order to prevent the high capacity of the battery and the deterioration of heavy load characteristics after storage, a nickel-silver alloy plating layer or a nickel-chromium alloy plating layer is formed on the rolled steel plate material on the surface that becomes the inner surface of the can, A method of reducing the internal resistance of the battery by reducing the internal resistance of the battery by increasing the contact area with the positive electrode mixture or conductive film by forming fine cracks by press drawing and ironing to form fine irregularities, After a nickel plating layer is formed and a silver plating layer is formed thereon, heat treatment is performed to form a nickel-silver plating layer, thereby reducing the plating crystals and increasing the hardness, further increasing the spacing between cracks. Thus, there has been proposed a battery can (see, for example, Patent Document 3) in which the contact area with the positive electrode mixture or the conductive coating is further increased to reduce the internal resistance of the battery.
しかし、電池容器内面に用いる鋼板面に直接形成させるニッケル−リン合金層は硬くて脆いために、絞り加工や絞りしごき加工を施して容器に成形加工する際に、下地の鋼が露出して電解液であるアルカリ溶液に対する耐食性が低下する恐れがある。同様に、特許文献２や特許文献３に記載の電池缶においても、プレス絞り加工して細かいひび割れを生じさせると、鋼素地が露出して電解液に用いられるアルカリ溶液に対する耐食性が低下する恐れがある。 However, since the nickel-phosphorus alloy layer directly formed on the steel plate surface used for the battery container inner surface is hard and brittle, when forming into a container by drawing or drawing ironing, the underlying steel is exposed and electrolyzed. There is a possibility that the corrosion resistance to the alkaline solution which is a liquid may be lowered. Similarly, in the battery cans described in Patent Document 2 and Patent Document 3, if a fine crack is generated by press drawing, the steel base may be exposed and the corrosion resistance against the alkaline solution used for the electrolyte may be reduced. is there.
本出願に関する先行技術文献情報として次のものがある。
本発明においては、絞り加工や絞りしごき加工を施して電池容器にプレス加工する場合に電池容器内面側のめっき層に鋼素地に達することのない微小クラックが発生し、アルカリ電池の正極合剤との密着性と接触抵抗が向上して、長期保存後に優れた電池性能を十分に発揮することを可能とする電池容器用めっき鋼板、その電池容器用めっき鋼板を用いた電池容器、およびその電池容器を用いた電池を提供することを目的とする。 In the present invention, when the battery container is pressed by drawing or squeezing and ironing, micro cracks that do not reach the steel substrate occur in the plating layer on the battery container inner surface side, and the positive electrode mixture of the alkaline battery and Improved adhesion and contact resistance of the battery container, and sufficient battery performance after long-term storage can be fully exhibited, a battery container using the battery container plated steel sheet, and the battery container It aims at providing the battery using this.
本発明の目的を達成するため、本発明の電池容器用めっき鋼板は、鋼板の電池容器内面となる側の鋼板上に下から順に、ニッケル層、コバルト層、銀層が形成されてなることを特徴とする電池容器用めっき鋼板（請求項１）、または
鋼板の電池容器内面となる側の鋼板上に下から順に、鉄−ニッケル合金層、ニッケル層、コバルト層、銀層が形成されてなることを特徴とする電池容器用めっき鋼板（請求項２）、または
鋼板の電池容器内面となる側の鋼板上に下から順に、鉄−ニッケル合金層、コバルト層、銀層が形成されてなることを特徴とする電池容器用めっき鋼板（請求項３）のいずれかである。
In order to achieve the object of the present invention, the plated steel sheet for battery containers according to the present invention is such that a nickel layer, a cobalt layer, and a silver layer are formed in order from the bottom on the steel sheet that is the inner surface of the battery container. An iron-nickel alloy layer, a nickel layer, a cobalt layer, and a silver layer are formed in order from the bottom on the plated steel sheet for battery containers (Claim 1) or the steel sheet on the side that is the battery container inner surface of the steel sheet. An iron-nickel alloy layer, a cobalt layer, and a silver layer are formed in order from the bottom on the plated steel sheet for battery containers (Claim 2), or the steel sheet on the side that is the battery container inner surface of the steel sheet. Any one of the plated steel sheets for battery containers (Claim 3).
また本発明の電池容器は、上記（請求項１〜３）のいずれかの電池容器用めっき鋼板を有底の筒型形状に成形加工してなる電池容器（請求項４）である。そして本発明の電池は、上記（請求項４）の電池容器を用いてなる電池（請求項５）である。 Moreover, the battery container of this invention is a battery container (Claim 4) formed by shape | molding the plated steel plate for battery containers in any one of the said (Claims 1-3) to a bottomed cylindrical shape. And the battery of this invention is a battery (Claim 5) using the battery container of said (Claim 4).
本発明の電池容器用めっき鋼板は、鋼板の電池容器内面となる側にニッケルめっきを施し、引き続いてコバルトめっきを施し、さらにその上に銀めっきを施してなるめっき鋼板、あるいはニッケルめっきを施し、次いで熱処理を施してニッケルめっき層の一部を鉄−ニッケル合金層に変換させるか、または鋼板素地上のニッケルめっき層の全てを鉄−ニッケル合金層を形成させた後、その上にコバルトめっきを施し、引き続いてさらにその上に銀めっきを施してなるめっき鋼板とすることにより、上記請求項1〜３に記載の電池容器用めっき鋼板を得ることができる。またその電池容器用めっき鋼板を成形加工してなる電池容器を用いることにより、電池保存後の放電性能に優れた電池を提供することが可能となる。さらに、電池容器内面となる側の最表面にアルカリ電解液に対する耐食性に優れ、展延性にも優れる銀層を設けることにより鋼素地が露出することがなくなり、アルカリ電解液中への鉄溶出が抑制されて電池容器内のガス圧上昇を抑制することが可能となる。 The plated steel sheet for battery containers according to the present invention is plated with nickel on the battery container inner surface side of the steel sheet, subsequently coated with cobalt, and further plated with silver or plated with nickel, or plated with nickel. Next, heat treatment is performed to convert a part of the nickel plating layer into an iron-nickel alloy layer, or after forming the iron-nickel alloy layer on the entire nickel plating layer on the steel plate, cobalt plating is formed thereon. The plated steel sheet for a battery container according to any one of claims 1 to 3 can be obtained by applying and subsequently forming a plated steel sheet obtained by further silver plating thereon. Moreover, it becomes possible to provide the battery excellent in the discharge performance after a battery preservation | save by using the battery container formed by shape | molding the plated steel plate for battery containers. Furthermore, by providing a silver layer with excellent corrosion resistance to alkaline electrolyte and excellent spreadability on the outermost surface on the battery container inner surface side, the steel substrate is not exposed and iron elution into the alkaline electrolyte is suppressed. This makes it possible to suppress an increase in gas pressure in the battery container.
本発明の電池容器用めっき鋼板の電池容器内面となる側に形成するコバルト層は、ニッケル層に比べてアルカリ電池の電解液に対する耐酸化性に優れ、またコバルト層上に設ける銀層もアルカリ電池の電解液に対する耐食性に優れ、かつ電気伝導性にも優れているために電池の接触抵抗も低下させることが可能となり、両者の相乗効果により電池保存後の放電特性が向上することを本発明の発明者らは見出した。さらに、従来のニッケルめっき鋼板を用いた電池においては、電池保存後の放電特性の劣化を防止するために、電池容器に成形加工した後に内面に黒鉛またはカーボンを主体とする導電皮膜を塗布し形成していたが、本発明においては電池容器内面となる側の最表面に銀層を設けたことにより、導電皮膜を省略しても従来の導電皮膜を形成したニッケルめっき鋼板による電池と同等以上の電池性能が得られる。また、本発明の電池容器用めっき鋼板による電池容器内面に導電皮膜を形成した場合は、電池性能はより一層向上させることが可能である。 The cobalt layer formed on the battery container inner surface side of the plated steel sheet for battery containers of the present invention is superior in oxidation resistance to alkaline battery electrolyte compared to the nickel layer, and the silver layer provided on the cobalt layer is also an alkaline battery. It is possible to reduce the contact resistance of the battery due to the excellent corrosion resistance to the electrolyte and the electrical conductivity, and the synergistic effect of both improves the discharge characteristics after storage of the battery. The inventors have found. In addition, in batteries using conventional nickel-plated steel sheets, a conductive film mainly composed of graphite or carbon is applied to the inner surface after forming into a battery container to prevent deterioration of discharge characteristics after battery storage. However, in the present invention, by providing a silver layer on the outermost surface on the side that becomes the battery container inner surface, even if the conductive film is omitted, the battery is equivalent to or better than the conventional nickel-plated steel sheet with the conductive film formed. Battery performance is obtained. Moreover, when a conductive film is formed on the inner surface of the battery container using the plated steel sheet for battery containers of the present invention, the battery performance can be further improved.
以下、本発明の内容を説明する。本発明の電池容器用めっき鋼板の基板となる鋼板としては、汎用の低炭素アルミキルド鋼（炭素量０．０１〜０．１５重量％）、またはニオブやチタンを添加した非時効性の極低炭素アルミキルド鋼（炭素量０．０１重量％未満）を用いる。これらの鋼の熱間圧延板を酸洗して表面のスケールを除去した後、常法により冷間圧延し次いで電解洗浄、焼鈍、調質圧延したものを基板として用いる。あるいは、冷間圧延し次いで電解洗浄後の未焼鈍材を基板として用いることもできる。この場合はニッケルめっき処理後に、鋼素地の焼鈍を兼ねたニッケルめっき層の拡散熱処理を１回の熱処理で行なう。 The contents of the present invention will be described below. As a steel plate used as a substrate for the plated steel plate for battery containers of the present invention, general-purpose low carbon aluminum killed steel (carbon content 0.01 to 0.15 wt%), or non-aging ultra-low carbon added with niobium or titanium. Aluminum killed steel (carbon content less than 0.01% by weight) is used. These steel hot-rolled plates are pickled to remove surface scales, then cold-rolled by a conventional method, and then subjected to electrolytic cleaning, annealing, and temper rolling as a substrate. Alternatively, an unannealed material that has been cold-rolled and then subjected to electrolytic cleaning can be used as a substrate. In this case, after the nickel plating process, the diffusion heat treatment of the nickel plating layer that also serves as the annealing of the steel substrate is performed by one heat treatment.
基板である鋼板の両面にまずニッケルめっきを施す。ニッケルめっきは、無光沢浴、もしくはこれに有機添加剤を含有させた半光沢浴を用いることが好ましい。ニッケルめっきのめっき厚は２〜２５ｇ／ｍ２の皮膜量であることが好ましい。ニッケルめっき厚が２ｇ／ｍ２未満では電池容器外面における耐食性が充分でなく、また２５ｇ／ｍ２を超えると耐食性は飽和に達し、不経済である。 First, nickel plating is performed on both surfaces of a steel plate as a substrate. For nickel plating, it is preferable to use a matte bath or a semi-gloss bath containing an organic additive. The plating thickness of the nickel plating is preferably a coating amount of 2 to 25 g / m 2 . When the nickel plating thickness is less than 2 g / m 2 , the corrosion resistance on the outer surface of the battery container is insufficient, and when it exceeds 25 g / m 2 , the corrosion resistance reaches saturation, which is uneconomical.
次いでニッケルめっきを施した鋼板を熱拡散処理を施してニッケルめっき層の一部または全部を鉄−ニッケル合金層に変換させた後、または熱拡散処理を施さずにニッケルめっきを施した後に引き続いて、コバルトめっきを施し、次いで銀めっきを施す。熱拡散処理は次に示すようにして行なう。すなわち、低炭素アルミキルド鋼による鋼板を用いた場合は箱型焼鈍法または連続焼鈍法のいずかの焼鈍法を用いることができるが、通常は箱型焼鈍法を用いて熱拡散処理する。極低炭素アルミキルド鋼による鋼板を用いた場合は、連続焼鈍法を用いて熱拡散処理するが、冷間圧延後の未焼鈍材を用いて、鋼素地の再結晶焼鈍とニッケルめっき層の熱拡散処理を１度の処理で行なうことが可能であり、工程の短縮化を図ることができる。熱拡散処理により形成する鉄−ニッケル合金層の量は、ニッケルめっき量および熱拡散処理の温度と時間を適宜選択することにより、調整することができる。箱型焼鈍法を用いる場合は４５０〜６５０℃、好ましくは５００〜６００℃の温度範囲で１〜６時間、均熱加熱する。４５０℃未満の加熱温度では鉄−ニッケル拡散層（合金層）が形成しない。６５０℃を超える温度で加熱すると鉄−ニッケル拡散層（合金層）は十分に形成されるものの、鋼素地が軟質化し過ぎてしまう。連続焼鈍法を用いる場合は６００〜８５０℃の温度範囲で１〜５分間加熱することが好ましい。 Subsequently, the steel plate subjected to nickel plating is subjected to a thermal diffusion treatment to convert a part or all of the nickel plating layer into an iron-nickel alloy layer, or subsequently after the nickel plating without the thermal diffusion treatment. Cobalt plating is performed, followed by silver plating. The thermal diffusion process is performed as follows. That is, when a steel plate made of low carbon aluminum killed steel is used, either a box-type annealing method or a continuous annealing method can be used, but usually a heat diffusion treatment is performed using a box-type annealing method. When using steel sheets made of ultra-low carbon aluminum killed steel, heat diffusion treatment is performed using a continuous annealing method, but using an unannealed material after cold rolling, recrystallization annealing of the steel base and thermal diffusion of the nickel plating layer The process can be performed by a single process, and the process can be shortened. The amount of the iron-nickel alloy layer formed by the thermal diffusion treatment can be adjusted by appropriately selecting the nickel plating amount and the temperature and time of the thermal diffusion treatment. When using a box-type annealing method, soaking is carried out at 450 to 650 ° C, preferably 500 to 600 ° C for 1 to 6 hours. An iron-nickel diffusion layer (alloy layer) is not formed at a heating temperature of less than 450 ° C. When heated at a temperature exceeding 650 ° C., the iron-nickel diffusion layer (alloy layer) is sufficiently formed, but the steel substrate becomes too soft. When using a continuous annealing method, it is preferable to heat in the temperature range of 600-850 degreeC for 1 to 5 minutes.
以上のようにして形成した鉄−ニッケル合金層またはニッケルめっき層の上にコバルトめっきを施す。コバルトめっきは、生産上の観点から公知のめっき浴を用いて、電気めっき法で形成させることが好ましい。コバルトめっきの皮膜量は０．５〜５ｇ／ｍ２の範囲とすることが好ましい。 Cobalt plating is performed on the iron-nickel alloy layer or nickel plating layer formed as described above. The cobalt plating is preferably formed by an electroplating method using a known plating bath from the viewpoint of production. The coating amount of cobalt plating is preferably in the range of 0.5 to 5 g / m 2 .
引き続いてコバルトめっき層上に銀めっきを施す。銀めっきに用いるめっき浴としてはシアン浴と非シアン浴があるが、毒性のないメタンスルホン酸銀−ヨウ化カリウム浴にスルファニル酸誘導体を添加した非シアン浴を用いることが好ましい。銀めっきの皮膜量は０．０５〜２ｇ／ｍ２の範囲で良好な導電性とガス発生抑制効果が得られる。皮膜量が０．０５ｇ／ｍ２未満では電池性能の十分な向上効果が得られず、２ｇ／ｍ２を超えると電池性能の向上効果が飽和して経済的に不利となる。 Subsequently, silver plating is performed on the cobalt plating layer. As a plating bath used for silver plating, there are a cyan bath and a non-cyan bath, but it is preferable to use a non-cyan bath obtained by adding a sulfanilic acid derivative to a non-toxic silver methanesulfonate-potassium iodide bath. Good electroconductivity and gas generation suppression effect can be obtained when the coating amount of silver plating is in the range of 0.05 to 2 g / m 2 . Not obtained sufficient effect of improving the battery performance in the coating amount is less than 0.05 g / m 2, when it exceeds 2 g / m 2 the effect of improving the battery performance is economically disadvantageous saturated.
以上のようにして、鋼板上にニッケルめっきを施し、次いで熱拡散処理を施して鉄−ニッケル合金層を形成させた後、または熱拡散処理を施さずにニッケルめっき後に引き続いてコバルトめっきを施し、さらに次いで銀めっきを施すことにより、図１〜図３に記載の断面構成を備えた本発明の電池容器用めっき鋼板が得られる。なお図１〜図３は、電池容器内面となる側の鋼素地から上の層構成を示したものである。電池容器外面に相当する側の層構成としては、鋼素地上にニッケル層、または鋼素地上に鉄−ニッケル拡散層（合金層）または、または鋼素地上に鉄ニッケル拡散層（合金層）とその上にニッケル層が形成される。 As described above, nickel plating is performed on the steel sheet, and then heat diffusion treatment is performed to form an iron-nickel alloy layer, or cobalt plating is subsequently performed after nickel plating without performing heat diffusion treatment, Furthermore, the plating steel plate for battery containers of this invention provided with the cross-sectional structure of FIGS. 1-3 is obtained by silver-plating then. In addition, FIGS. 1-3 shows the upper layer structure from the steel base of the side used as the battery container inner surface. As the layer structure on the side corresponding to the outer surface of the battery case, a nickel layer on the steel base, an iron-nickel diffusion layer (alloy layer) on the steel base, or an iron nickel diffusion layer (alloy layer) on the steel base A nickel layer is formed thereon.
これらのめっき鋼板において、ニッケルめっき後に熱処理を施した場合は、通常１．０〜１．５％の圧延率で調質圧延し、本発明の電池容器用めっき鋼板とするが、電池容器に成形加工する際に発生するストレッチャーストレインが支障にならない場合は調質圧延を省くことが可能である。なお、鋼板の電池容器の外面となる片面に、ニッケルめっきのみのめっき層に替えて、電池容器の内面となる他の片面に施す上記と同様の各めっき層を形成させてもよい。 In these plated steel sheets, when heat treatment is performed after nickel plating, temper rolling is usually performed at a rolling rate of 1.0 to 1.5% to obtain the plated steel sheet for battery containers of the present invention. If the stretcher strain generated during processing does not hinder, temper rolling can be omitted. In addition, it may replace with the plating layer only of nickel plating on the single side | surface used as the outer surface of the battery container of a steel plate, and may form each plating layer similar to the above given to the other one side used as the inner surface of a battery container.
本発明の電池容器は、上記の電池容器用めっき鋼板を、絞り加工法、絞りしごき加工法（ＤＩ加工法）、絞りストレッチ加工法（ＤＴＲ加工法）、または絞り加工後ストレッチ加工としごき加工を併用する加工法を用いて、有底の筒型形状に成形加工して得られる。筒型形状としては、底面が円、楕円、または長方形や正方形などの多角形の形状であり、用途に応じて側壁の高さを適宜選択した筒型形状に成形加工する。このようにして得られる電池容器に正極合剤、負極活物質等を充填して電池とする。 The battery container of the present invention is obtained by subjecting the above-described plated steel sheet for a battery container to a drawing process, a drawing ironing process (DI processing method), a drawing stretch processing method (DTR processing method), or a drawing process as a stretching process. It is obtained by forming into a bottomed cylindrical shape using the processing method used in combination. As the cylindrical shape, the bottom surface is a circle, an ellipse, or a polygonal shape such as a rectangle or a square, and is molded into a cylindrical shape with the side wall height appropriately selected according to the application. The battery container thus obtained is filled with a positive electrode mixture, a negative electrode active material, and the like to obtain a battery.
以下、実施例にて本発明を詳細に説明する。
[電池容器用めっき鋼板の作成]
めっき基板として、表１に化学組成を示す熱間圧延済みの低炭素アルミキルド鋼（Ｉ）または極低炭素アルミキルド鋼（ＩＩ）を用い、下記のイ）〜ハ）に示す工程を経て電池容器用めっき鋼板を作成した。
イ）低炭素アルミキルド鋼（Ｉ）→冷間圧延→電解洗浄→焼鈍（箱型焼鈍または連続焼鈍）→調質圧延→ニッケルめっき→コバルトめっき→銀めっき
ロ）低炭素アルミキルド鋼（Ｉ）→冷間圧延→電解洗浄→焼鈍（箱型焼鈍または連続焼鈍）→調質圧延→ニッケルめっき→拡散熱処理（箱型焼鈍または連続焼鈍）→調質圧延→コバルトめっき→銀めっき
ハ）極低炭素アルミキルド鋼（ＩＩ）→冷間圧延→電解洗浄→ニッケルめっき→焼鈍兼拡散熱処理（連続焼鈍）→調質圧延→コバルトめっき→銀めっき
Hereinafter, the present invention will be described in detail with reference to examples.
[Creation of plated steel sheets for battery containers]
As the plating substrate, hot-rolled low carbon aluminum killed steel (I) or extremely low carbon aluminum killed steel (II) whose chemical composition is shown in Table 1 is used, and the battery container is subjected to the steps shown in the following a) to c). A plated steel sheet was created.
B) Low carbon aluminum killed steel (I) → Cold rolling → Electrolytic cleaning → Annealing (box annealing or continuous annealing) → Temper rolling → Nickel plating → Cobalt plating → Silver plating b) Low carbon aluminum killed steel (I) → Cold Hot rolling → Electrolytic cleaning → Annealing (box annealing or continuous annealing) → Temper rolling → Nickel plating → Diffusion heat treatment (box annealing or continuous annealing) → Temper rolling → Cobalt plating → Silver plating c) Extremely low carbon aluminum killed steel (II)-> cold rolling-> electrolytic cleaning-> nickel plating-> annealing and diffusion heat treatment (continuous annealing)-> temper rolling-> cobalt plating-> silver plating
上記のＩまたはＩＩの鋼種の熱間圧延板に、常法により冷間圧延、電解洗浄を施して０．２５ｍｍの板厚を有する冷間圧延板とした後、鋼種Ｉの場合は箱型焼鈍炉で均熱温度６４０〜６８０℃で均熱時間８時間の焼鈍を行った。次いで以下に示す条件でニッケルめっき、コバルトめっきおよび銀めっきを施した。鋼種ＩＩの場合はニッケルめっきを施した後、連続焼鈍炉で加熱温度７８０℃、加熱時間１〜２分の焼鈍を行った。次いで以下に示す条件でコバルトめっきおよび銀めっきを施した。 A hot rolled sheet of the above steel grade I or II is subjected to cold rolling and electrolytic cleaning by a conventional method to obtain a cold rolled sheet having a thickness of 0.25 mm. Annealing was performed in a furnace at a soaking temperature of 640 to 680 ° C. for a soaking time of 8 hours. Next, nickel plating, cobalt plating, and silver plating were performed under the following conditions. In the case of steel type II, after nickel plating, annealing was performed in a continuous annealing furnace at a heating temperature of 780 ° C. and a heating time of 1 to 2 minutes. Next, cobalt plating and silver plating were performed under the following conditions.
＜ニッケルめっき＞
浴組成 硫酸ニッケル ３００ｇ／Ｌ
塩化ニッケル ３５ｇ／Ｌ
ホウ酸 ４０ｇ／Ｌ
ピット抑制剤（ラウリル硫酸ナトリウム） ０．４ｍＬ／Ｌ
陽極 ニッケルペレット（チタンバスケットにＩＮＣＯ(株）製Sペレットを充填 しポリプロピレン製アノードバッグを装着）
攪拌 空気撹拌
ｐＨ ４．０〜４．６
浴温 ５５〜６０℃
電流密度 １０A／ｄｍ2
<Nickel plating>
Bath composition Nickel sulfate 300g / L
Nickel chloride 35g / L
Boric acid 40g / L
Pit inhibitor (sodium lauryl sulfate) 0.4mL / L
Anode Nickel Pellet (Titanium basket filled with S pellets from INCO Corporation and equipped with polypropylene anode bag)
Stirring air stirring
pH 4.0-4.6
Bath temperature 55-60 ° C
Current density 10A / dm 2
＜コバルトめっき＞
浴組成 硫酸コバルト ３００ｇ／Ｌ
塩化コバルト ３０ｇ／Ｌ
塩化ナトリウム ２５ｇ／Ｌ
ホウ酸 ４５ｇ／Ｌ
陽極 チタン板に白金めっきを施した不溶性陽極
攪拌 めっき浴の循環
ｐＨ ３．７〜４．３
浴温 ５０℃
電流密度 ２．５A／ｄｍ2
<Cobalt plating>
Bath composition Cobalt sulfate 300g / L
Cobalt chloride 30g / L
Sodium chloride 25g / L
Boric acid 45g / L
Anode Insoluble anode with platinum plating on titanium plate Stirring Circulation of plating bath pH 3.7 to 4.3
Bath temperature 50 ° C
Current density 2.5A / dm 2
＜銀めっき＞
浴組成 銀含有有機酸塩（ダインシルバーＮＥＣ（大和化成研究所(株)製）
２００ｇ／Ｌ
有機酸（錯塩）（ダインシルバーＡＧＩ（大和化成研究所(株)製）
５００ｇ／Ｌ
有機添加剤（平滑剤）（ダインシルバーＡＧＨ（大和化成研究所(株)製）
２５ｇ／Ｌ
陽極 銀板
攪拌 めっき浴の循環
浴温 ４０±３℃
電流密度 ５A／ｄｍ2
<Silver plating>
Bath composition Silver-containing organic acid salt
200g / L
Organic acid (complex salt) (Dyne Silver AGI (manufactured by Daiwa Kasei Laboratories))
500g / L
Organic additive (smoothing agent) (Dyne Silver AGH (manufactured by Daiwa Kasei Laboratories))
25g / L
Anode Silver plate Stirring Circulation of plating bath Bath temperature 40 ± 3 ℃
Current density 5A / dm 2
ロ）に示した工程において、ニッケルめっき後に拡散熱処理を施す場合、箱型焼鈍法を用いた場合は、窒素−水素系保護ガス雰囲気下で均熱温度５００〜６００℃、均熱時間６〜８時間の熱処理を施した。また、ハ）に示した工程において、ニッケルめっき後に鋼素地の焼鈍を兼ねためっき層の拡散熱処理を１回の熱処理で行なう場合は、連続焼鈍法を用いて、加熱温度７８０℃、加熱時間１〜２分間の熱処理を行なった。 In the process shown in (b), when the diffusion heat treatment is performed after nickel plating, or when the box annealing method is used, the soaking temperature is 500 to 600 ° C. and the soaking time is 6 to 8 in a nitrogen-hydrogen protective gas atmosphere. Time heat treatment was applied. In addition, in the process shown in c), when the diffusion heat treatment of the plating layer that also serves as the annealing of the steel substrate is performed after nickel plating in one heat treatment, a continuous annealing method is used, and the heating temperature is 780 ° C. and the heating time is 1 A heat treatment of ˜2 minutes was performed.
以上のようにして表２に示す電池容器用めっき鋼板の試料（試料番号１〜１０）を作成した。また、低炭素アルミキルド鋼（Ｉ）を用い比較用にニッケルめっきを施したままの試料（試料番号１１）、およびニッケルめっき後に熱拡散処理した試料（試料番号１２）、およびニッケルめっきを施した後、ニッケル−リン合金めっきを施した試料（試料番号１３）、さらにニッケルめっきに次いでニッケル−リン合金めっきを施した後、熱処理を行なった試料（試料番号１４）を作成した。ニッケル−リン合金めっきは下記の条件で実施した。
＜ニッケル−リン合金めっき＞
浴組成 硫酸ニッケル ３００ｇ／Ｌ
塩化ニッケル ４５ｇ／Ｌ
ホウ酸 ４０ｇ／Ｌ
亜燐酸 １０ｇ／Ｌ
陽極 ニッケルペレット（チタンバスケットにＩＮＣＯ(株）製Ｓペレットを充填 しポリプロピレン製アノードバッグを装着）
攪拌 空気撹拝
ｐＨ １．５〜２．０
浴温 ５５〜６０℃
電流密度 １０Ａ／ｄｍ２
As described above, samples (sample numbers 1 to 10) of plated steel sheets for battery containers shown in Table 2 were prepared. Moreover, the sample (sample number 11) with nickel plating for comparison using low carbon aluminum killed steel (I), the sample (sample number 12) heat-treated after nickel plating, and after nickel plating Then, a sample (sample number 13) subjected to nickel-phosphorus alloy plating and a sample (sample number 14) subjected to heat treatment after nickel-phosphorous alloy plating following nickel plating were prepared. Nickel-phosphorus alloy plating was performed under the following conditions.
<Nickel-phosphorus alloy plating>
Bath composition Nickel sulfate 300g / L
Nickel chloride 45g / L
Boric acid 40g / L
Phosphorous acid 10g / L
Anode Nickel Pellets (Titanium basket filled with S pellets from INCO Corporation and equipped with polypropylene anode bag)
Stirring air stirring
pH 1.5-2.0
Bath temperature 55-60 ° C
Current density 10A / dm 2
[電池容器の作成]
これらの試料番号１〜１４の試料から５７ｍｍ径でブランクを打ち抜いた後、鉄−ニッケル合金層とニッケル層のみを設けた側が容器外面となるようにして、１０段の絞り加工により、外径１３．８ｍｍ、高さ４９．３ｍｍの円筒形のＬＲ６型電池（単三型電池）容器に成形加工した。本発明のめっき鋼板の試料の一部（試料番号１〜６）、および比較用の試料（試料番号１１〜１４）による容器の内面には、黒鉛粉末を主成分とする塗料を塗布し乾燥させて導電皮膜を形成させた。
[Create battery container]
After blanking a blank with a diameter of 57 mm from the samples of Sample Nos. 1 to 14, the outer diameter 13 was obtained by ten-stage drawing so that the side on which only the iron-nickel alloy layer and the nickel layer were provided was the outer surface of the container. It was molded into a cylindrical LR6 type battery (AA size battery) container having a height of 4 mm and a height of 49.3 mm. A paint mainly composed of graphite powder is applied to the inner surface of a part of the sample of the plated steel sheet of the present invention (sample numbers 1 to 6) and the sample for comparison (sample numbers 11 to 14) and dried. Thus, a conductive film was formed.
[電池の作成]
この電池容器を用いて、以下のようにしてアルカリマンガン電池を作成した。二酸化マンガンと黒鉛を１０：１の比率で採取し、水酸化カリウム（１０モル）を添加混合して正極合剤を作成した。次いでこの正極合剤を金型中で加圧して所定寸法のドーナツ形状の正極合剤ペレットに成形し、黒鉛粉末を主剤とした導電物質を内面に塗布した電池容器に圧挿入した。次に、負極集電棒をスポット溶接した負極板を電池容器に装着した。次いで、電池容器に圧挿入した正極合剤ペレットの内周に沿うようにしてビニロン製織布からなるセパレータを挿入し、亜鉛粒と酸化亜鉛を飽和させた水酸化カリウムからなる負極ゲルを電池容器内に充填した。さらに、負極板に絶縁体のガスケットを装着して電池容器内に挿入した後、カシメ加工してアルカリマンガン電池を作成した。
[Create battery]
Using this battery container, an alkaline manganese battery was prepared as follows. Manganese dioxide and graphite were collected at a ratio of 10: 1, and potassium hydroxide (10 mol) was added and mixed to prepare a positive electrode mixture. Next, this positive electrode mixture was pressed in a mold to form a doughnut-shaped positive electrode mixture pellet having a predetermined size, and was press-inserted into a battery container having a conductive material mainly composed of graphite powder applied on the inner surface. Next, the negative electrode plate spot-welded with the negative electrode current collector rod was attached to the battery container. Next, a separator made of vinylon woven cloth is inserted along the inner circumference of the positive electrode mixture pellet press-inserted into the battery container, and the negative electrode gel made of potassium hydroxide saturated with zinc particles and zinc oxide is put into the battery container. Filled in. Further, an insulating gasket was attached to the negative electrode plate and inserted into the battery container, followed by caulking to prepare an alkaline manganese battery.
[特性評価]
以上のようにして試料番号１〜１４の試料から作成した電池容器を用いて作成した電池の特性を、以下のようにして評価した。
[Characteristic evaluation]
The characteristics of the batteries prepared using the battery containers prepared from the samples Nos. 1 to 14 as described above were evaluated as follows.
＜短絡電流＞
電池を８０℃で３日間放置した後、電池に電流計を接続して閉回路を設けて電流値を測定し、これを短絡電流とした。短絡電流が大であるほど特性が良好であることを示す。
<Short-circuit current>
After leaving the battery at 80 ° C. for 3 days, an ammeter was connected to the battery, a closed circuit was provided, and the current value was measured, which was defined as a short-circuit current. It shows that a characteristic is so favorable that a short circuit current is large.
＜放電特性＞
電池を８０℃で３日間放置した後、電池を１．５Ａの一定電流に放電し、終止電圧が０．９Ｖに到達するまでの時間を放電時間として測定した。放電時間が長いほど放電特性が良好であることを示す。
<Discharge characteristics>
After the battery was left at 80 ° C. for 3 days, the battery was discharged to a constant current of 1.5 A, and the time until the end voltage reached 0.9 V was measured as the discharge time. The longer the discharge time, the better the discharge characteristics.
＜間歇放電特性＞
重付加間歇放電の評価として、２Ａで０．５秒放電した後に０．２５Ａで２９．５秒放電する操作を１サイクルとして、このサイクルを繰り返し、電圧が１．０Ｖに到達するまでのサイクル数を測定した。サイクル数が多いはど間歇放電特性が良好であることを示す。これらの評価結果を表４に示す。
<Intermittent discharge characteristics>
As an evaluation of the double-added intermittent discharge, an operation of discharging at 2A for 0.5 seconds and then discharging at 0.25A at 29.5 seconds is defined as one cycle, and this cycle is repeated until the voltage reaches 1.0V. Was measured. A high number of cycles indicates that the intermittent discharge characteristics are good. These evaluation results are shown in Table 4.
表４に示すように、本発明の電池容器用めっき鋼板を用いて電池容器を作成し、内面に導電皮膜を塗布せずに用いた場合は、従来のニッケルめっき鋼板を用いて電池容器を作成し、次いで内面に導電皮膜を塗布して用いた場合に比べて短絡電流、放電特性、間歇放電特性のいずれにおいても同等以上の特性を示す。また、本発明の電池容器用めっき鋼板を用いて電池容器を作成し、次いで内面に導電皮膜を塗布して用いた場合は、これらの特性がさらに一層向上する。 As shown in Table 4, when a battery container is made using the plated steel sheet for battery containers of the present invention and used without applying a conductive film on the inner surface, a battery container is made using a conventional nickel-plated steel sheet Then, compared with the case where a conductive film is applied to the inner surface, the same or better characteristics are exhibited in any of the short-circuit current, discharge characteristics, and intermittent discharge characteristics. In addition, when a battery container is prepared using the plated steel sheet for a battery container of the present invention, and then a conductive film is applied to the inner surface, these characteristics are further improved.
鋼板上にニッケルめき層とその上にコバルト層、さらにその上に銀層を形成してなるか、あるいは鋼板上に鉄−ニッケル合金層または／およびニッケル層とその上にコバルト層とさらにその上に銀層を形成してなる本発明の電池容器用めっき鋼板は、絞り加工や絞りしごき加工を施して容器に成形加工する際にめっき層が剥離したりひび割れが生じることがなく、また表面が耐アルカリ性および導電性に優れているので、デジタルカメラなどの重負荷放電が求められる用途における電池特性に優れ、高性能電池用の容器および高性能電池として好適に適用することができる。また、従来の電池容器内面におけるような導電性皮膜を形成せずとも、従来の導電性皮膜を形成した電池容器と同等以上の優れた特性を示すので、導電性塗料を塗布して乾燥させる工程を省略することが可能となり、低コストで高性能電池を製造することができる。 A nickel plating layer and a cobalt layer thereon and a silver layer thereon are formed on the steel plate, or an iron-nickel alloy layer and / or nickel layer and a cobalt layer thereon and further thereon. The plated steel sheet for battery containers according to the present invention formed by forming a silver layer on the surface is free from peeling or cracking of the plated layer when formed into a container by drawing or drawing ironing, and the surface is Since it is excellent in alkali resistance and conductivity, it is excellent in battery characteristics in applications where heavy load discharge is required, such as a digital camera, and can be suitably applied as a container for high performance batteries and a high performance battery. Also, without forming a conductive film as on the inner surface of a conventional battery container, it exhibits excellent characteristics equivalent to or better than a battery container formed with a conventional conductive film. Can be omitted, and a high-performance battery can be manufactured at low cost.
Claims (5)
A battery comprising the battery container according to claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006011700A JP2006307321A (en) | 2005-03-30 | 2006-01-19 | Plated steel sheet for battery vessel, battery vessel using the plated steel sheet for battery vessel, and battery using the battery vessel |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005097917 | 2005-03-30 | ||
| JP2006011700A JP2006307321A (en) | 2005-03-30 | 2006-01-19 | Plated steel sheet for battery vessel, battery vessel using the plated steel sheet for battery vessel, and battery using the battery vessel |
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| Publication Number | Publication Date |
|---|---|
| JP2006307321A true JP2006307321A (en) | 2006-11-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006011700A Withdrawn JP2006307321A (en) | 2005-03-30 | 2006-01-19 | Plated steel sheet for battery vessel, battery vessel using the plated steel sheet for battery vessel, and battery using the battery vessel |
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| Country | Link |
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| JP (1) | JP2006307321A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101115592B1 (en) | 2011-05-19 | 2012-03-05 | 주식회사 에이엔씨코리아 | Non-cyanide silver plating solution and method for forming plating using it |
| US11230781B1 (en) | 2020-07-29 | 2022-01-25 | Toyota Jidosha Kabushiki Kaisha | Method for forming silver film |
-
2006
- 2006-01-19 JP JP2006011700A patent/JP2006307321A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101115592B1 (en) | 2011-05-19 | 2012-03-05 | 주식회사 에이엔씨코리아 | Non-cyanide silver plating solution and method for forming plating using it |
| US11230781B1 (en) | 2020-07-29 | 2022-01-25 | Toyota Jidosha Kabushiki Kaisha | Method for forming silver film |
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