JP3834260B2 - Ni-plated steel sheet for battery cans - Google Patents
Ni-plated steel sheet for battery cans Download PDFInfo
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- JP3834260B2 JP3834260B2 JP2002130791A JP2002130791A JP3834260B2 JP 3834260 B2 JP3834260 B2 JP 3834260B2 JP 2002130791 A JP2002130791 A JP 2002130791A JP 2002130791 A JP2002130791 A JP 2002130791A JP 3834260 B2 JP3834260 B2 JP 3834260B2
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- 229910000831 Steel Inorganic materials 0.000 title claims description 29
- 239000010959 steel Substances 0.000 title claims description 29
- 238000007747 plating Methods 0.000 claims description 73
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 20
- 238000009792 diffusion process Methods 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 67
- 238000005260 corrosion Methods 0.000 description 18
- 230000007797 corrosion Effects 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910018104 Ni-P Inorganic materials 0.000 description 2
- 229910018536 Ni—P Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910001096 P alloy Inorganic materials 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- 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
- Sealing Battery Cases Or Jackets (AREA)
- Electroplating Methods And Accessories (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、電池缶に用いられるメッキ鋼板素材に関し、更に詳しくは、電池缶の耐食性、電池特性、表面摺動性を改善しうる、メッキ鋼板素材に関するものである。
【０００２】
【従来の技術】
一般に電池缶用の素材として、Ｎｉメッキされた鋼板が使用される。従来Ｎｉメッキは、缶に加工した後のいわゆるバレルメッキによって行われてきたが、缶内面へのＮｉメッキの付着が十分ではなく品質上の不安定性の問題があることから、先メッキ鋼板を缶に加工する方法に置き換わりつつある。先メッキ鋼板の場合、Ｎｉメッキ層が硬く延展性に乏しいことから、プレス加工性に劣り、また加工時にメッキが剥離して耐食性が劣化しやすい等の問題があった。
【０００３】
この問題に対し、Ｎｉメッキ後熱処理することでメッキと地鉄の界面にＦｅ−Ｎｉ拡散層を形成して密着性を向上させると同時に、Ｎｉを再結晶、軟質化してメッキ層の延展性を向上させる方法が知られており、プレス加工性や耐食性は大幅に改善される（例えば特開昭６１−２３５５９４号公報）。
【０００４】
しかしながら、前述の従来技術では、Ｎｉメッキ層が再結晶、軟質化している結果として、電池製造過程において電池缶を高速搬送する際、電池缶外面どおしの接触における摺動性が必ずしも十分でなく、缶の流れ性が劣り生産性を悪化させる場合がある。
【０００５】
特公平５−２５９５８号公報では、Ｎｉメッキ後、更にＮｉ−Ｐ合金メッキを施して熱処理することにより、Ｆｅ−Ｎｉ拡散層と再結晶、軟質化したＮｉメッキ層の上層に更に硬質なＮｉ−Ｐ合金メッキ層を有する耐食性と耐疵つき性に優れたＮｉメッキ鋼板が示されている。この鋼板は、前述の電池缶外面の摺動性も十分である。
【０００６】
【発明が解決しようとする課題】
前記の特公平５−２５９５８号公報の技術は、張り出し等の単純な成形において良好な耐食性を保持しているが、実際の電池缶に加工した場合の耐食性は必ずしも十分でない。これは、上層の硬質なメッキ層のクラックが下層まで波及することや、剥離した硬質なメッキ層が金型に付着して電池缶表層を疵付けること等によると考えられる。また更に、類似の原因と推定されるが、前記の鋼板を使用して成形した電池缶は、貯蔵後の接触抵抗値が高く、電池特性を悪化させやすいといった問題もあることが判明した。
【０００７】
そこで本発明は、耐食性、電池特性、摺動性に優れた電池缶用のＮｉメッキ鋼板の提供を目的とする。
【０００８】
【課題を解決するための手段】
課題で述べたような耐食性、電池特性、摺動性の改善のためには、特定のメッキ層構成を採用し、特に缶外面になる面の表層の摩擦係数を低くすることが重要であることを見出し本発明に至った。
【０００９】
すなわち本発明の要旨とするところは、電池缶用のメッキ鋼板であって、缶外面になる面に、再結晶軟質化されたＮｉメッキ層と更にその上層に未再結晶の軟質Ｎｉメッキ層を有することを特徴とし、再結晶軟質化されたＮｉメッキ層が、地鉄とＦｅ−Ｎｉ拡散層を介して形成され、また未再結晶のＮｉメッキ層が、無光沢メッキによって形成されたものであることが望ましい。望ましいＮｉメッキ量は、未再結晶のＮｉメッキ層が、Ｎｉとして０．１ｇ／ｍ2以上、再結晶軟質化されたＮｉメッキ層は、Ｆｅ−Ｎｉ拡散層のＮｉと合計して９ｇ／ｍ2以上としたことである。
【００１０】
具体的には、次の通りである。
【００１１】
（１） 電池缶用のメッキ鋼板であって、缶外面になる面に、地鉄とＦｅ−Ｎｉ拡散層を介して形成されている再結晶軟質化されたＮｉメッキ層と、更にその上層に未再結晶の無光沢Ｎｉメッキ層を有することを特徴とする電池缶用Ｎｉメッキ鋼板。
【００１３】
（２） 未再結晶の無光沢Ｎｉメッキ層の付着量が、Ｎｉとして０．１ｇ／ｍ2以上であることを特徴とする前記（１）に記載の電池缶用Ｎｉメッキ鋼板。
【００１４】
（３） 再結晶軟質化されたＮｉメッキ層の付着量が、Ｆｅ−Ｎｉ拡散層のＮｉと合計して９ｇ／ｍ2以上であることを特徴とする前記（１）または（２）のいずれかに記載の電池缶用Ｎｉメッキ鋼板。
【００１５】
（４） 缶内面になる面に、Ｎｉメッキ層またはＦｅ−Ｎｉ拡散層を有し、その付着量がＮｉ量として１ｇ／ｍ2以上であることを特徴とする前記（１）から（３）のいずれかに記載の電池缶用Ｎｉメッキ鋼板。
【００１６】
（５） 缶内面になる面に、Ｎｉメッキ層及びＦｅ−Ｎｉ拡散層を有し、その付着量がＮｉ量として両層の合計で１ｇ／ｍ2以上であることを特徴とする前記（１）から（３）のいずれかに記載の電池缶用Ｎｉメッキ鋼板。
【００１７】
（６） 缶内面になる面に、Ｆｅ−Ｎｉ拡散層とその上層に未再結晶の無光沢Ｎｉメッキ層を有することを特徴とする前記（５）に記載の電池缶用Ｎｉメッキ鋼板。
【００１８】
【発明の実施の形態】
以下、本発明を詳細に説明する。
【００１９】
まず、本発明における、電池缶外面に相当する面の構成要件について説明する。
【００２０】
外面になる面には再結晶軟質化されたＮｉメッキ層と更にその上層に未再結晶の軟質Ｎｉメッキ層を有することが必要であり、再結晶軟質化されたＮｉメッキ層が、地鉄とＦｅ−Ｎｉ拡散層を介して形成され、また未再結晶のＮｉメッキ層が、無光沢メッキによって形成されたものであることが望ましい。
【００２１】
再結晶軟質化されたＮｉメッキ層とは、Ｎｉメッキ後に熱処理を行って形成したもので、熱処理の過程で地鉄との界面に一部Ｆｅ−Ｎｉ拡散合金層を形成することがより好ましい。この様な構成によって耐食性は良好となるが、電池缶とした際の表面の摺動性が十分でない。
【００２２】
このため、本発明においては、前記再結晶軟質化されたＮｉメッキ層の上層に未再結晶の軟質Ｎｉメッキ層を形成することが必要である。未再結晶とは、メッキ後に熱処理による再結晶処理を行っていない、メッキままであることを意味する。軟質Ｎｉメッキとは、Ｐ、Ｃ、Ｓ等との微量合金メッキであるところの通常の硬質メッキではないことを意味し、光沢添加剤、レベリング剤、ピンホール抑制剤等の有機系添加物を含まない無光沢Ｎｉメッキがその代表例である。光沢メッキ、半光沢メッキは添加剤中のＣ、Ｓ等起因で硬質化するため、本発明では用いることはできない。
【００２３】
未再結晶の軟質Ｎｉメッキは、その皮膜単みの硬度（ビッカース５ｇ）を測定すると、２３０〜３００程度の値が得られる。一方、再結晶軟質化されたＮｉメッキ層単みの硬度（ビッカース５ｇ）を測定すると１００〜２００程度となり、以上のような微妙に異なる硬度のメッキ層が積層されることによって極めて良好な耐食性と表面摺動性が得られる。
【００２４】
なお、再結晶軟質化されたＮｉメッキ層の上層に、Ｎｉ−Ｐ合金メッキ、光沢Ｎｉメッキ等の硬質メッキ層を設けると、単純な表面の摺動性は良好になるも、実際の電池缶プレスのような条件ではメッキ層に多数の割れが発生し、耐食性が低下する。また同様の理由と推定されるが、電池缶の接触抵抗も増加して電池特性が悪化する。
【００２５】
再結晶軟質化されたＮｉメッキ層の望ましい皮膜量としては、Ｆｅ−Ｎｉ拡散層がある場合は拡散層のＮｉと合計して、９ｇ／ｍ2以上である。これ未満では耐食性が悪化する。なお、ここでのＮｉ量が少ないと熱処理の条件によっては、再結晶軟質化されたＮｉメッキ層が形成されず、ＮｉのすべてがＦｅ−Ｎｉ拡散層となりやすく、この場合耐食性が悪化するため、好ましくは、１２ｇ／ｍ2以上のＮｉ付着量が望ましい。なお、Ｎｉの上限はコストの観点から規制され、通常は４０ｇ／ｍ2程度である。
【００２６】
未再結晶の軟質Ｎｉメッキ層の望ましい皮膜量としては、０．１ｇ／ｍ2以上であり、これ未満では摺動性が悪化する。Ｎｉの上限はコストの観点から規制され、通常は１８ｇ／ｍ2程度である。
【００２７】
次に、缶内面になる面について、説明する。缶内面になる面には、外面になる面ほど高度な耐食性は要求されず、Ｎｉとして１ｇ／ｍ2程度以上のメッキ層を有していれば十分である。ここでのＮｉメッキ層については、何ら限定はなく、光沢メッキ、無光沢メッキ、いずれでも可能である。またＮｉメッキ層であっても、Ｆｅ−Ｎｉ拡散層であっても、前者の複合であっても構わない。複合の場合には、両層の合計のＮｉ量が１ｇ／ｍ2以上であればよい。なお、Ｎｉ量の上限はコストの観点から決定すればよく、通常は１８ｇ／ｍ2程度である。
。なお電池特性の観点から、最も好ましい形態として、Ｆｅ−Ｎｉ拡散層の上層に、更に未再結晶の軟質Ｎｉメッキ層が形成されている構成を例示できる。
【００２８】
【実施例】
以下に具体例によって本発明を詳細に説明する。
【００２９】
以下の本発明の実施例１〜６及び比較例１〜４の例では、いずれも、板厚０．３ｍｍのＮｂ−Ｔｉ−Ｓｕｌｃ鋼（未再結晶鋼板）を原板とし、Ｎｉメッキ（１回目）→熱処理→Ｎｉメッキ（２回目）→調質圧延、の順でサンプルを製造した。
【００３０】
Ｎｉメッキ（１回目）、熱処理、Ｎｉメッキ（２回目）のそれぞれの条件を表１に示す。Ｎｉメッキの付着量については、電池缶の「外面になる面」／「内面になる面」、それぞれについて表示している。
【００３１】
【表１】
（メッキ層の状態解析）
缶内、外面になる面のメッキ層の状態を、断面ＳＥＭ観察、及び、ＧＤＳ分析により観察した。この結果は表２に示す。
（性能評価方法）
前記鋼板サンプルをプレス加工し、通常のＬＲ０６型アルカリマンガン電池用の缶を製造し、この缶で評価を行った。
▲１▼ 耐食性：正極端子部を上に向けて、塩水噴霧試験（ＪＩＳ−Ｚ−２３７１）を３時間行い、赤錆発生状況を目視観察した。錆なしを「○」、極軽微な錆（点状錆が１０個まで）ありを「△」、錆ありを「×」と評価した。
▲２▼ 摺動性：ｈｅｉｄｏｎ１４型試験装置を用い、缶胴側面を１０ｍｍφステンレス球で２０ｇの荷重で摺動し、動摩擦係数を求めた。０．１５未満を「○」、０．１５超０．２未満を「△」、０．２以上を「×」と評価した。
▲３▼ 電池特性（接触抵抗）：電池缶を６０℃９０％ＲＨに２０日間放置した後、山崎精機研究所製電気接点シュミレータＣＲＳ−１を用い、荷重１００ｇにて接触抵抗を測定した。１０ｍΩ未満を「○」、１０ｍΩ以上２０ｍΩ未満を「△」、２０ｍΩ以上を「×」と評価した。
▲４▼ 電池特性（放電時間）：ＬＲ０６型アルカリマンガン電池を作製し、初期及び６０℃×４０日経時後で、１．５Ａ一定放電により０．９Ｖ到達時間を求め、初期値を１００として、経時後で８０以上を「○」、９０以上を「◎」とした。
【００３３】
以上の評価結果を表２に示す。表２に示すように、本発明の実施例では良好な耐食性、摺動性、電池特性が得られた。これに対して、比較例では、耐食性、摺動性、電池特性のいずれかで良好な性質が得られなかった。
【００３４】
【表２】
【発明の効果】
本発明は、電池缶用のメッキ鋼板であって、缶外面になる面に、地鉄とＦｅ−Ｎｉ拡散層を介して形成されている再結晶軟質化されたＮｉメッキ層と更にその上層に未再結晶の軟質Ｎｉメッキ層を有することにより、耐食性、電池特性、摺動性に優れたメッキ鋼板素材が得られた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a plated steel sheet material used for a battery can, and more particularly to a plated steel sheet material that can improve the corrosion resistance, battery characteristics, and surface slidability of the battery can.
[0002]
[Prior art]
In general, a Ni-plated steel sheet is used as a material for a battery can. Conventionally, Ni plating has been carried out by so-called barrel plating after processing into a can, but since the Ni plating adheres to the inner surface of the can and is not sufficient, there is a problem of instability in quality. It is being replaced by the method of processing. In the case of a pre-plated steel sheet, since the Ni plating layer is hard and poor in spreadability, the press workability is inferior, and the plating is peeled off during processing and the corrosion resistance is liable to deteriorate.
[0003]
To solve this problem, heat treatment after Ni plating forms a Fe-Ni diffusion layer at the interface between the plating and the base iron to improve adhesion, and at the same time recrystallizes and softens Ni to increase the spreadability of the plating layer. A method of improving is known, and press workability and corrosion resistance are greatly improved (for example, JP-A 61-235594).
[0004]
However, in the above-described prior art, as a result of the Ni plating layer being recrystallized and softened, when the battery can is conveyed at high speed during the battery manufacturing process, the slidability in contact between the outer surfaces of the battery can is not always sufficient. In some cases, the flowability of the can is poor and the productivity is deteriorated.
[0005]
In Japanese Examined Patent Publication No. 5-25958, after Ni plating, Ni-P alloy plating is further applied and heat treatment is performed, so that a harder Ni-- layer is formed on the Fe-Ni diffusion layer and the recrystallized and softened Ni plating layer. An Ni-plated steel sheet having a P alloy plating layer and excellent in corrosion resistance and scratch resistance is shown. This steel plate has sufficient slidability on the outer surface of the battery can.
[0006]
[Problems to be solved by the invention]
The technology of the above Japanese Patent Publication No. 5-25958 maintains good corrosion resistance in simple molding such as overhanging, but the corrosion resistance when processed into an actual battery can is not always sufficient. This is considered to be due to the cracks in the upper hard plating layer spreading to the lower layer, the peeled hard plating layer adhering to the mold and brazing the battery can surface. Furthermore, although it is presumed that the cause is similar, it has been found that the battery can formed using the steel sheet has a problem that the contact resistance value after storage is high and the battery characteristics are easily deteriorated.
[0007]
Then, this invention aims at provision of the Ni plating steel plate for battery cans excellent in corrosion resistance, battery characteristics, and slidability.
[0008]
[Means for Solving the Problems]
In order to improve the corrosion resistance, battery characteristics, and slidability as described in the topic, it is important to adopt a specific plating layer configuration, and in particular to lower the coefficient of friction of the surface layer on the outer surface of the can And found the present invention.
[0009]
That is, the gist of the present invention is a plated steel plate for a battery can, and a recrystallized and softened Ni plating layer is formed on the outer surface of the can and an unrecrystallized soft Ni plating layer is further formed thereon. The recrystallized and softened Ni plating layer is formed through the base iron and the Fe-Ni diffusion layer, and the non-recrystallized Ni plating layer is formed by matte plating. It is desirable to be. Desirable Ni plating amount is 0.1 g / m 2 or more of Ni in an unrecrystallized Ni plating layer, and 9 g / m in total of Ni in a re-crystallized softened Ni plating layer. 2 or more.
[0010]
Specifically, it is as follows.
[0011]
(1) A plated steel sheet for battery cans, on the surface that becomes the outer surface of the can, a recrystallized and softened Ni plating layer formed on the surface of the can through a Fe—Ni diffusion layer, and further on the upper layer A Ni-plated steel sheet for battery cans, comprising an unrecrystallized matte Ni-plated layer.
[0013]
( 2 ) The Ni-plated steel sheet for battery cans according to ( 1 ) above, wherein the adhesion amount of the non -recrystallized matte Ni plating layer is 0.1 g / m 2 or more as Ni.
[0014]
( 3 ) Either of (1) and (2) above, wherein the amount of adhesion of the recrystallized and softened Ni plating layer is 9 g / m 2 or more in total with Ni in the Fe—Ni diffusion layer A Ni-plated steel sheet for battery cans according to claim 1.
[0015]
( 4 ) The above-mentioned (1) to (3), wherein the inner surface of the can has a Ni plating layer or a Fe—Ni diffusion layer, and the amount of adhesion is 1 g / m 2 or more as the amount of Ni. The Ni-plated steel sheet for battery cans according to any one of the above.
[0016]
(5) to the surface to be the inner surface of the can, has a Ni plated layer and Fe-Ni diffusion layer, wherein, characterized in that the adhesion amount is 1 g / m 2 or more in total of both layers as Ni amount (1 To Ni-plated steel sheet for battery cans according to any one of (3) to (3) .
[0017]
( 6 ) The Ni-plated steel sheet for battery cans according to (5) above, wherein an Fe-Ni diffusion layer and an unrecrystallized matte Ni-plated layer are provided on the upper surface of the can-inner surface.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0019]
First, the structural requirements of the surface corresponding to the outer surface of the battery can in the present invention will be described.
[0020]
It is necessary to have a recrystallized and softened Ni plating layer on the surface to be the outer surface and an unrecrystallized soft Ni plating layer on the upper layer. It is desirable that the Ni-plated layer formed through the Fe—Ni diffusion layer and not recrystallized is formed by matte plating.
[0021]
The recrystallized and softened Ni plating layer is formed by performing a heat treatment after Ni plating, and it is more preferable that a part of the Fe—Ni diffusion alloy layer is formed at the interface with the ground iron during the heat treatment. Such a structure provides good corrosion resistance, but the surface slidability when the battery can is made is not sufficient.
[0022]
Therefore, in the present invention, it is necessary to form an unrecrystallized soft Ni plating layer on the recrystallized and softened Ni plating layer. Unrecrystallized means that the recrystallization treatment by heat treatment is not performed after plating, and the plating remains as it is. Soft Ni plating means that it is not a normal hard plating that is a trace alloy plating with P, C, S, etc., and organic additives such as gloss additives, leveling agents, pinhole inhibitors, etc. A typical example is non-glossy Ni plating. Since gloss plating and semi-gloss plating harden due to C, S, etc. in the additive, they cannot be used in the present invention.
[0023]
When the non-recrystallized soft Ni plating measures the hardness of a single film (Vickers 5 g), a value of about 230 to 300 is obtained. On the other hand, when the hardness of the recrystallized and softened Ni plating layer (Vickers 5 g) is measured, it becomes about 100 to 200, and extremely good corrosion resistance can be obtained by laminating the plating layers with slightly different hardness as described above. Surface slidability is obtained.
[0024]
If a hard plating layer such as Ni-P alloy plating or bright Ni plating is provided on the recrystallized and softened Ni plating layer, simple surface slidability will be improved, but actual battery cans Under conditions such as pressing, a large number of cracks occur in the plated layer, and the corrosion resistance is reduced. The same reason is presumed, but the contact resistance of the battery can increases and the battery characteristics deteriorate.
[0025]
The desirable coating amount of the recrystallized and softened Ni plating layer is 9 g / m 2 or more in total with Ni in the diffusion layer when there is an Fe—Ni diffusion layer. If it is less than this, corrosion resistance will deteriorate. If the amount of Ni here is small, depending on the conditions of the heat treatment, the recrystallized and softened Ni plating layer is not formed, and all of Ni is likely to be a Fe-Ni diffusion layer, and in this case, the corrosion resistance deteriorates. Preferably, a Ni adhesion amount of 12 g / m 2 or more is desirable. The upper limit of Ni is regulated from the viewpoint of cost, and is usually about 40 g / m 2 .
[0026]
A desirable coating amount of the non-recrystallized soft Ni plating layer is 0.1 g / m 2 or more, and if it is less than this, the slidability deteriorates. The upper limit of Ni is regulated from the viewpoint of cost, and is usually about 18 g / m 2 .
[0027]
Next, the surface that becomes the inner surface of the can will be described. The surface that becomes the inner surface of the can is not required to have a higher degree of corrosion resistance than the surface that becomes the outer surface, and it is sufficient if the Ni has a plating layer of about 1 g / m 2 or more. The Ni plating layer here is not limited at all, and any of gloss plating and matte plating is possible. Further, it may be a Ni plating layer, a Fe—Ni diffusion layer, or the former composite. In the case of a composite, the total amount of Ni in both layers may be 1 g / m 2 or more. The upper limit of the Ni amount may be determined from the viewpoint of cost, and is usually about 18 g / m 2 .
. From the viewpoint of battery characteristics, the most preferable form is a configuration in which a non-recrystallized soft Ni plating layer is further formed on the upper layer of the Fe—Ni diffusion layer.
[0028]
【Example】
Hereinafter, the present invention will be described in detail by way of specific examples.
[0029]
In the following Examples 1 to 6 and Comparative Examples 1 to 4 of the present invention, Nb-Ti-Sulc steel (non-recrystallized steel plate) having a thickness of 0.3 mm is used as an original plate, and Ni plating (first time) ) → Heat treatment → Ni plating (second time) → temper rolling.
[0030]
Table 1 shows conditions for Ni plating (first time), heat treatment, and Ni plating (second time). About the adhesion amount of Ni plating, it has displayed about "the surface used as an outer surface" / "the surface used as an inner surface" of a battery can.
[0031]
[Table 1]
(Plating layer state analysis)
The state of the plating layer on the inside and outside of the can was observed by cross-sectional SEM observation and GDS analysis. The results are shown in Table 2.
(Performance evaluation method)
The steel plate sample was pressed to produce a can for a normal LR06 type alkaline manganese battery, and the can was evaluated.
(1) Corrosion resistance: A salt spray test (JIS-Z-2371) was conducted for 3 hours with the positive electrode terminal facing upward, and the occurrence of red rust was visually observed. The evaluation was “◯” for no rust, “Δ” for extremely light rust (up to 10 spot-like rusts), and “×” for rust.
(2) Sliding property: Using a heidon 14 type test apparatus, the side surface of the can body was slid with a 10 mmφ stainless steel ball under a load of 20 g, and the dynamic friction coefficient was determined. Less than 0.15 was evaluated as “◯”, more than 0.15 and less than 0.2 as “Δ”, and 0.2 or more as “x”.
(3) Battery characteristics (contact resistance): The battery can was left at 60 ° C. and 90% RH for 20 days, and then contact resistance was measured at a load of 100 g using an electrical contact simulator CRS-1 manufactured by Yamazaki Seiki Laboratory. Less than 10 mΩ was evaluated as “◯”, 10 mΩ or more and less than 20 mΩ was evaluated as “Δ”, and 20 mΩ or more was evaluated as “X”.
(4) Battery characteristics (discharge time): An LR06-type alkaline manganese battery was prepared, and after reaching the initial value and after 60 ° C. × 40 days, 0.9V arrival time was obtained by constant 1.5 A discharge, and the initial value was set to 100. After the lapse of time, 80 or more was designated as “◯” and 90 or more as “◎”.
[0033]
The above evaluation results are shown in Table 2. As shown in Table 2, good corrosion resistance, slidability, and battery characteristics were obtained in the examples of the present invention. On the other hand, in the comparative example, good properties were not obtained in any of corrosion resistance, slidability, and battery characteristics.
[0034]
[Table 2]
【The invention's effect】
The present invention is a plated steel plate for a battery can, and a recrystallized and softened Ni plating layer formed on the surface that becomes the outer surface of the can via a ground iron and an Fe-Ni diffusion layer, and further on the upper layer By having an unrecrystallized soft Ni plating layer, a plated steel sheet material excellent in corrosion resistance, battery characteristics, and slidability was obtained.
Claims (6)
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| JP2002130791A JP3834260B2 (en) | 2002-01-18 | 2002-05-02 | Ni-plated steel sheet for battery cans |
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| JP2002-10276 | 2002-01-18 | ||
| JP2002130791A JP3834260B2 (en) | 2002-01-18 | 2002-05-02 | Ni-plated steel sheet for battery cans |
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| JP2008041527A (en) * | 2006-08-09 | 2008-02-21 | Matsushita Electric Ind Co Ltd | Battery can, and battery using it |
| KR20130139363A (en) * | 2011-05-10 | 2013-12-20 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Ni-plated metal sheet, welded structure, and method for making battery material |
| JP6349192B2 (en) * | 2014-08-07 | 2018-06-27 | Fdk株式会社 | Steel plate for battery electrode terminal and battery constructed using the same |
| CN110945155B (en) * | 2017-07-28 | 2022-06-07 | 杰富意钢铁株式会社 | Steel sheet for battery outer can, and battery |
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| JP2000026992A (en) * | 1989-08-31 | 2000-01-25 | Katayama Tokushu Kogyo Kk | Ni-PLATED STEEL SHEET |
| JP2001279490A (en) * | 2000-03-30 | 2001-10-10 | Nisshin Steel Co Ltd | ONE SIDE Ni PLATED STEEL SHEET HAVING HIGH LUSTER AND REDUCED CONTACT RESISTANCE FOR NEGATIVE AND POSITIVE POLE CANS OF LITHIUM BUTTON CELL |
| JP4247338B2 (en) * | 2000-03-30 | 2009-04-02 | Ｄｏｗａメタルテック株式会社 | Electrical contact material and manufacturing method thereof |
| JP4808834B2 (en) * | 2000-08-04 | 2011-11-02 | 東洋鋼鈑株式会社 | Surface-treated steel sheet for battery case |
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