JP4051012B2 - Ni-plated steel sheet for battery cans - Google Patents
Ni-plated steel sheet for battery cans Download PDFInfo
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- JP4051012B2 JP4051012B2 JP2003312604A JP2003312604A JP4051012B2 JP 4051012 B2 JP4051012 B2 JP 4051012B2 JP 2003312604 A JP2003312604 A JP 2003312604A JP 2003312604 A JP2003312604 A JP 2003312604A JP 4051012 B2 JP4051012 B2 JP 4051012B2
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- recrystallized
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- 229910000831 Steel Inorganic materials 0.000 title claims description 40
- 239000010959 steel Substances 0.000 title claims description 40
- 238000007747 plating Methods 0.000 claims description 79
- 238000009792 diffusion process Methods 0.000 claims description 45
- 239000000654 additive Substances 0.000 claims description 36
- 230000000996 additive effect Effects 0.000 claims description 36
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 35
- 230000003746 surface roughness Effects 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 72
- 238000005260 corrosion Methods 0.000 description 21
- 230000007797 corrosion Effects 0.000 description 21
- 238000011282 treatment Methods 0.000 description 15
- 238000005096 rolling process Methods 0.000 description 13
- 235000019592 roughness Nutrition 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000010438 heat treatment Methods 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
- 238000000034 method Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000007864 aqueous 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
- 239000012467 final product Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 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
- 230000004913 activation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 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
- Electroplating Methods And Accessories (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Description
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。 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.
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。 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.
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（例えば特許文献１）。 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, Patent Document 1).
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。また、プレス加工においても、金型との摺動性が十分でなく、プレス性を悪化させる場合もある。 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. Also in the press working, the slidability with the mold is not sufficient, and the pressability may be deteriorated.
特許文献２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く、また、前記の鋼板を使用して成形した電池缶は、貯蔵後の極端子部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。 According to Patent Document 2, a Ni-P alloy plating layer that is harder on the Fe-Ni diffusion layer and the recrystallized and softened Ni plating layer by performing Ni-P alloy plating and heat treatment after Ni plating. A Ni-plated steel sheet having excellent corrosion resistance and scratch resistance is shown. This steel plate has sufficient slidability on the outer surface of the battery can as described above, but the corrosion resistance when processed into an actual battery can is not always sufficient, and the battery can formed using the steel plate, It has been found that there is a problem that the contact resistance value of the electrode terminal portion after storage is high and the battery characteristics are easily deteriorated.
特許文献３では、缶外面の最表層に光沢Ｎｉ層あるいは、光沢Ｎｉ−Ｃｏ合金メッキ層を有する電池缶用メッキ鋼板が示されており、良好な摺動性が得られる。しかしながら、前記の鋼板を使用して成形した電池缶は、貯蔵後の極端子部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。 Patent Document 3 discloses a plated steel sheet for battery cans having a bright Ni layer or a bright Ni-Co alloy plating layer as the outermost layer on the outer surface of the can, and good slidability is obtained. However, it has been found that the battery can formed using the steel plate has a problem that the contact resistance value of the electrode terminal part after storage is high and the battery characteristics are easily deteriorated.
そこで本発明は、耐食性、摺動性および接触抵抗に優れた電池缶用のＮｉメッキ鋼板および電池缶の提供を目的とする。 Then, this invention aims at provision of the Ni plating steel plate and battery can for battery cans which were excellent in corrosion resistance, slidability, and contact resistance.
課題で述べたような耐食性、摺動性および接触抵抗の改善のためには、特定のメッキ層構成を採用し、特に缶外面になる面のメッキ層状態の制御が重要である。本発明者は、
Ｆｅ−Ｎｉ拡散層、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層を有し、更にその上層に光沢添加剤あるいは半光沢添加剤を含有するＮｉメッキ層を設け、かつその表面粗度が０．２μｍ以上であれば、耐食性、摺動性および接触抵抗に優れた電池缶用のＮｉメッキ鋼板が得られることを見出し本発明に至った。
In order to improve the corrosion resistance, slidability and contact resistance as described in the problem, it is important to adopt a specific plating layer configuration, and in particular, to control the plating layer state on the outer surface of the can. The inventor
Fe-Ni diffusion layer, or Fe-Ni diffusion layer and an Ni plating layer recrystallized and softened on the upper layer, and further provided with an Ni plating layer containing a glossy additive or a semi-gloss additive on the upper layer, And if the surface roughness was 0.2 micrometer or more, it discovered that the Ni plating steel plate for battery cans excellent in corrosion resistance, slidability, and contact resistance was obtained, and it came to this invention.
すなわち本発明の要旨とするところは、電池缶外面に相当する面に、Ｆｅ−Ｎｉ拡散層、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層を有し、更にその上層に光沢添加剤含有Ｎｉメッキ層または半光沢剤含有Ｎｉメッキ層を有し、かつその表面粗度Ｒａが０．２μｍ以上であることを特徴とする電池缶用Ｎｉメッキ鋼板である。前記光沢添加剤または半光沢添加剤含有Ｎｉメッキ層の付着量は、０．５ｇ／ｍ2以上であり、かつ、その下層のＮｉ量（Ｆｅ−Ｎｉ拡散層のＮｉ量、または、Ｆｅ−Ｎｉ拡散層とその上層の再結晶軟質化されたＮｉメッキ層の合計のＮｉ量）以下であることが望ましい。 That is, the gist of the present invention is that the surface corresponding to the outer surface of the battery can has an Fe—Ni diffusion layer, or an Fe—Ni diffusion layer and an Ni plating layer recrystallized and softened thereon, and further A Ni-plated steel sheet for battery cans having a bright additive-containing Ni-plated layer or a semi-brightener-containing Ni-plated layer as an upper layer and having a surface roughness Ra of 0.2 μm or more. The adhesion amount of the gloss additive or semi-gloss additive-containing Ni plating layer is 0.5 g / m 2 or more, and the Ni amount in the lower layer (Ni amount of Fe—Ni diffusion layer or Fe—Ni) The total amount of Ni in the diffusion layer and the recrystallized and softened Ni plating layer on the diffusion layer is preferably equal to or less than the above.
本発明においては、少なくとも電池缶の外面となる面に、Ｆｅ−Ｎｉ拡散層、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層を有し、更にその上層に光沢添加剤含有Ｎｉメッキ層または半光沢添加剤含有Ｎｉメッキ層を有することが必要である。更にその表面粗度Ｒａは０．２μｍ以上であることが必要である。 In the present invention, at least the outer surface of the battery can has an Fe—Ni diffusion layer, or an Fe—Ni diffusion layer and an Ni plating layer recrystallized and softened on the upper layer, and a gloss addition is added to the upper layer. It is necessary to have an agent-containing Ni plating layer or a semi-bright additive-containing Ni plating layer. Furthermore, the surface roughness Ra needs to be 0.2 μm or more.
Ｆｅ−Ｎｉ拡散層、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層は、耐食性を確保するために、必須である。その望ましい付着量は、Ｎｉとして（Ｆｅ−Ｎｉ拡散層のＮｉ量、または、Ｆｅ−Ｎｉ拡散層とその上層の再結晶軟質化されたＮｉメッキ層の合計のＮｉ量）５〜４５ｇ／ｍ2であり、５ｇ／ｍ2未満では耐食性が不足しやすく、４５ｇ／ｍ2超でも効果が飽和して不経済である。より高度な耐食性の観点からは、Ｆｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層を有することが望ましい。 The Fe-Ni diffusion layer or the Ni-plated layer recrystallized and softened on the Fe-Ni diffusion layer and the upper layer thereof is essential to ensure corrosion resistance. The desirable adhesion amount is 5 to 45 g / m 2 as Ni (Ni amount in the Fe—Ni diffusion layer or the total Ni amount of the Fe—Ni diffusion layer and the recrystallized and softened Ni plating layer). If it is less than 5 g / m 2 , the corrosion resistance tends to be insufficient, and if it exceeds 45 g / m 2 , the effect is saturated and uneconomical. From the viewpoint of higher corrosion resistance, it is desirable to have a Fe—Ni diffusion layer and an Ni plating layer recrystallized and softened thereon.
前記のＦｅ−Ｎｉ拡散層、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層の上層に、光沢添加剤含有Ｎｉメッキ層または半光沢添加剤含有Ｎｉメッキ層を有し、かつその表面粗度Ｒａが０．２μｍ以上あれば、優れた摺動性と良好な接触抵抗も得ることができる。特に、そのメカニズムは明らかでないが、湿潤環境下で経時しても接触抵抗の悪化はきわめて少ない。ここで前述の表面粗度については、鋼板最終製品としての粗度Ｒａが０．２μｍ以上であれば良く、この条件を満たす限りにおいては、冷間圧延後の原板の段階で調整された粗度であってもかまわないし、光沢添加剤含有Ｎｉメッキ層または半光沢添加剤含有Ｎｉメッキ層を施す前、あるいは後のいずれの段階で付与されたものであっても構わない。 A gloss additive-containing Ni plating layer or a semi-gloss additive-containing Ni plating layer is formed on the Fe-Ni diffusion layer or the upper layer of the Fe-Ni diffusion layer and the recrystallized and softened Ni plating layer. If the surface roughness Ra is 0.2 μm or more, excellent slidability and good contact resistance can be obtained. In particular, the mechanism is not clear, but the contact resistance is hardly deteriorated even with aging in a humid environment. Here, as for the surface roughness described above, the roughness Ra as the steel plate final product may be 0.2 μm or more. As long as this condition is satisfied, the roughness adjusted at the stage of the original sheet after cold rolling. It may also be applied before or after applying the bright additive-containing Ni plating layer or the semi-bright additive-containing Ni plating layer.
前記の光沢添加剤含有Ｎｉメッキ層または半光沢添加剤含有Ｎｉメッキ層の付着量は、０．５ｇ／ｍ2以上が望ましく、これ未満では摺動性の改善効果が低い場合がある。また、上限としては、下層のＮｉ量（Ｆｅ−Ｎｉ拡散層のＮｉ量、または、Ｆｅ−Ｎｉ拡散層とその上層の再結晶軟質化されたＮｉメッキ層の合計のＮｉ量）以下であることが望ましい。これは、下層のＮｉ量と上層Ｎｉ量のバランスによっては、外観と耐食性が劣化する場合があるからである。すなわち、上層の高硬度（下層に比較し）のＮｉ量が、下層の低硬度（上層に比較し）のＮｉ量を超えると、加工時にクラックが入りやすく、耐食性が悪化する場合があるからである。 The adhesion amount of the gloss additive-containing Ni plating layer or the semi-gloss additive-containing Ni plating layer is desirably 0.5 g / m 2 or more, and if it is less than this, the effect of improving the slidability may be low. Also, the upper limit is lower than the lower Ni amount (Ni amount in the Fe—Ni diffusion layer or the total Ni amount of the Fe—Ni diffusion layer and the recrystallized and softened Ni plating layer). Is desirable. This is because the appearance and corrosion resistance may be deteriorated depending on the balance between the lower layer Ni amount and the upper layer Ni amount. That is, if the amount of Ni in the upper layer of high hardness (compared to the lower layer) exceeds the amount of Ni in the lower layer (compared to the upper layer), cracks are likely to occur during processing, and corrosion resistance may deteriorate. is there.
電池缶の内面となる面には、前述の外面となる面と同じ構成をとることももちろん可能であり、また違う構成とすることも可能である。違う構成とする場合には、Ｆｅ−Ｎｉ拡散層、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層を有することが、耐食性、電池特性の点から望ましい。 Of course, the inner surface of the battery can may have the same configuration as the outer surface, or may have a different configuration. In the case of a different configuration, it is desirable from the viewpoint of corrosion resistance and battery characteristics to have an Fe—Ni diffusion layer, or an Fe—Ni diffusion layer and an Ni plating layer recrystallized and softened thereon.
以上の状態を得るためには、Ｎｉメッキ、拡散処理、光沢添加剤または半光沢添加剤含有Ｎｉメッキ、の順で処理し、圧延による粗度調整はこのいずれの工程間にあっても良い。以下では、Ｎｉメッキ、拡散処理、圧延による粗度調整、光沢添加剤または半光沢添加剤含有Ｎｉメッキの順で処理する場合を例として、その条件について各工程毎に以下説明する。 In order to obtain the above state, Ni plating, diffusion treatment, gloss additive or semi-gloss additive-containing Ni plating are processed in this order, and the roughness adjustment by rolling may be between these steps. Below, the case where it processes in order of Ni plating, a spreading | diffusion process, the roughness adjustment by rolling, and a gloss additive or semi-gloss additive containing Ni plating is demonstrated for every process as an example below.
（メッキ下地鋼板）
下地鋼板はＮｉメッキを施すことができるものであれば特に限定はないが、電池ケース用に加工に供されることを考慮すると、極低炭素鋼にＴｉ，Ｎｂ等を単独または複合添加したものや、低炭素Ａｌキルド鋼やＢ添加低炭素鋼等が好ましい。また、冷間圧延後の未再結晶の鋼板でも、再結晶焼鈍後の鋼板でも更に調質圧延後の鋼板でも用いることが出来るが、本発明においてはＦｅ−Ｎｉ拡散層の存在が必須であるので、Ｎｉメッキ後に拡散処理と下地鋼板の再結晶焼鈍を同時に行うことが経済的観点から好ましい。この観点から、下地鋼板としては冷間圧延後の未再結晶の鋼板を用いるのが本発明における最も有利な実施形態である。
(Plating base steel plate)
The base steel plate is not particularly limited as long as it can be Ni-plated, but considering that it is used for processing for battery cases, ultra low carbon steel with Ti, Nb, etc. added alone or in combination Further, low carbon Al killed steel, B-added low carbon steel and the like are preferable. In addition, it is possible to use a non-recrystallized steel sheet after cold rolling, a steel sheet after recrystallization annealing, or a steel sheet after temper rolling, but in the present invention, the presence of an Fe-Ni diffusion layer is essential. Therefore, it is preferable from an economical viewpoint that the diffusion treatment and the recrystallization annealing of the base steel sheet are simultaneously performed after the Ni plating. From this viewpoint, the most advantageous embodiment of the present invention is to use a non-recrystallized steel sheet after cold rolling as the base steel sheet.
（メッキ前処理）
Ｎｉメッキを施すための前処理であれば、何ら限定はなく、通常の処理（脱脂、酸洗等）を行えばよい。
(Plating pretreatment)
There is no limitation as long as it is a pretreatment for applying Ni plating, and ordinary treatments (degreasing, pickling, etc.) may be performed.
（Ｎｉメッキ）
メッキに先だって、通常の前処理（脱脂、酸洗等）を必要に応じて行う。メッキは、無光沢Ｎｉメッキ浴を用いることが耐食性の観点から望ましい。具体的には、ｗａｔｔ浴を例示できる。Ｎｉメッキの付着量は、外面になる面、内面になる面で同一でもよいが、差厚でもよい。
(Ni plating)
Prior to plating, normal pretreatment (degreasing, pickling, etc.) is performed as necessary. For plating, it is desirable to use a matte Ni plating bath from the viewpoint of corrosion resistance. Specifically, a watt bath can be illustrated. The adhesion amount of the Ni plating may be the same on the outer surface or the inner surface, but may be a difference thickness.
（熱拡散処理）
不活性ガスまたは還元性のガス雰囲気中で熱処理して、Ｆｅ−Ｎｉ拡散層を形成する。具体的には、７００〜８５０℃程度の温度で均熱時間２０〜６０ｓｅｃ程度の処理を行う。この際、Ｎｉメッキ量が１０ｇ／ｍ2程度以上であれば、条件にもよるが、Ｆｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層が形成される。なお、下地鋼板として未再結晶鋼板を使用している時は、ここでの熱処理を鋼板の再結晶温度以上とすることで熱拡散処理と鋼板の再結晶焼鈍を同時に行うことができる。
(Thermal diffusion treatment)
Heat treatment is performed in an inert gas or reducing gas atmosphere to form a Fe—Ni diffusion layer. Specifically, the treatment is performed at a temperature of about 700 to 850 ° C. for a soaking time of about 20 to 60 seconds. At this time, if the Ni plating amount is about 10 g / m 2 or more, although depending on the conditions, a Fe—Ni diffusion layer and a recrystallized Ni plating layer formed thereon are formed. In addition, when the non-recrystallized steel plate is used as the base steel plate, the heat diffusion treatment and the recrystallization annealing of the steel plate can be simultaneously performed by setting the heat treatment here to the recrystallization temperature or higher of the steel plate.
（調質圧延）
圧延によって表面粗度を調整する。最終製品の表面粗度Ｒａが所定の値になるように、適度な粗さのロールを用いて行えば良い。表裏等粗度であっても、異粗度であってもよく、用途に応じてロールの粗度を調整して圧延することができる。
(Temper rolling)
The surface roughness is adjusted by rolling. What is necessary is just to perform using the roll of moderate roughness so that the surface roughness Ra of a final product may become a predetermined value. Roughness such as front and back surfaces or different roughness may be used, and rolling can be performed by adjusting the roughness of the roll according to the application.
（光沢添加剤または半光沢添加剤含有Ｎｉメッキ）
本メッキに先だって、通常の前処理（脱脂、酸洗等）を必要に応じて行う。光沢添加剤または半光沢添加剤含有Ｎｉメッキは、通常のＮｉメッキ浴、例えばｗａｔｔ浴に市販の光沢添加剤または半光沢添加剤を含有させた浴で処理する。本メッキは必要とする面にのみ通電して形成すれば良い。
(Gloss additive or semi-gloss additive-containing Ni plating)
Prior to the main plating, normal pretreatment (degreasing, pickling, etc.) is performed as necessary. The bright additive or semi-bright additive-containing Ni plating is processed in a normal Ni plating bath, for example, a bath in which a commercially available bright additive or semi-bright additive is contained in a watt bath. The plating may be formed by energizing only the necessary surface.
本発明によって、耐食性、摺動性および接触抵抗に優れた電池缶用のＮｉメッキ鋼板の提供が可能となった。上記本発明の電池缶用Ｎｉメッキ鋼板を用いてなる電池缶は、耐食性、摺動性および接触抵抗に優れた性質を有するものである。 According to the present invention, it is possible to provide a Ni-plated steel sheet for a battery can excellent in corrosion resistance, slidability and contact resistance. The battery can made from the Ni-plated steel sheet for battery can of the present invention has excellent properties such as corrosion resistance, slidability and contact resistance.
以下に実施例によって本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail by way of examples.
本発明例１〜６および比較例１〜３
板厚０．２５ｍｍのＮｂ−Ｔｉ−Ｓｕｌｃ鋼（未再結晶鋼板）を原板とし、無光沢Ｎｉメッキ→拡散処理→調質圧延→半光沢添加剤含有Ｎｉメッキの手順でサンプルを製造した。無光Ｎｉメッキは、無光沢ワット浴（硫酸ニッケル：３５０ｇ／リットル＋塩化ニッケル：７０ｇ／リットル＋ホウ酸：４５ｇ／リットル）によって行った。拡散処理は、連続焼鈍炉にて無酸化条件で８００℃均熱４０ｓｅｃの条件で行った（この条件を表１中「ｓｔｄ」と表記）。調質圧延は、２スタンド圧延機にて、各種粗度のロールを用い、ドライ圧延した。半光沢添加剤含有Ｎｉメッキは、先の無光沢ワット浴（硫酸ニッケル：３５０ｇ／リットル＋塩化ニッケル：７０ｇ／リットル＋ホウ酸：４５ｇ／リットル）に市販のアセチレン系半光沢添加剤を添加した浴で行った。なお、半光沢添加剤入Ｎｉメッキに先だって、５％ＮａＯＨによる脱脂処理、つづけて５％硫酸水溶液により表面活性化処理を行った。なお、無光沢Ｎｉメッキ、半光沢添加剤入Ｎｉメッキそれぞれの付着量は表１に示すとおりである。また最終製品の表面粗度Ｒａも表１に示すとおりである。
Invention Examples 1-6 and Comparative Examples 1-3
Samples were produced in the order of matte Ni plating → diffusion treatment → temper rolling → semi-gloss additive-containing Ni plating using Nb—Ti—Sulc steel (non-recrystallized steel plate) having a thickness of 0.25 mm as an original plate. Non-light Ni plating was performed by a matte Watt bath (nickel sulfate: 350 g / liter + nickel chloride: 70 g / liter + boric acid: 45 g / liter). The diffusion treatment was performed in a continuous annealing furnace under non-oxidizing conditions and 800 ° C. soaking conditions of 40 sec (this condition is expressed as “std” in Table 1). The temper rolling was dry-rolled using a roll having various roughnesses in a two-stand rolling mill. Semi-gloss additive-containing Ni plating is a bath obtained by adding a commercially available acetylenic semi-gloss additive to the previous matte watt bath (nickel sulfate: 350 g / liter + nickel chloride: 70 g / liter + boric acid: 45 g / liter). I went there. Prior to Ni plating with a semi-gloss additive, a degreasing treatment with 5% NaOH was performed, followed by a surface activation treatment with a 5% sulfuric acid aqueous solution. In addition, the adhesion amounts of the matte Ni plating and the semi-gloss additive-added Ni plating are as shown in Table 1. The surface roughness Ra of the final product is also as shown in Table 1.
本発明例７〜８および比較例４
半光沢添加剤含有Ｎｉメッキに替わり、光沢添加剤入Ｎｉメッキを行う以外は、先の例と全く同一に処理した。光沢添加剤含有Ｎｉメッキは、無光沢ワット浴（硫酸ニッケル：３５０ｇ／リットル＋塩化ニッケル：７０ｇ／リットル＋ホウ酸：４５ｇ／リットル）に市販の含窒素系光沢添加剤を添加した浴で行った。無光沢Ｎｉメッキ、光沢添加剤入Ｎｉメッキそれぞれの付着量は表１に示すとおりである。
Invention Examples 7 to 8 and Comparative Example 4
Instead of the semi-gloss additive-containing Ni plating, the same treatment as in the previous example was performed except that Ni plating with a gloss additive was performed. The bright additive-containing Ni plating was performed in a bath obtained by adding a commercially available nitrogen-containing bright additive to a matte Watt bath (nickel sulfate: 350 g / liter + nickel chloride: 70 g / liter + boric acid: 45 g / liter). . Table 1 shows the adhesion amounts of the matte Ni plating and the Ni plating with gloss additive.
比較例５
板厚０．２５ｍｍのＮｂ−Ｔｉ−Ｓｕｌｃ鋼（未再結晶鋼板）を原板とし、無光沢Ｎｉメッキ→拡散処理→調質圧延の手順でサンプルを製造した。無光沢Ｎｉメッキおよび拡散処理および調質圧延は、先の例（本発明例１〜６および比較例１〜３）と全く同一に行った。
Comparative Example 5
A sample was manufactured in the order of matte Ni plating → diffusion treatment → temper rolling using Nb—Ti—Sulc steel (non-recrystallized steel plate) having a thickness of 0.25 mm as an original plate. Matte Ni plating, diffusion treatment and temper rolling were performed exactly as in the previous examples (Invention Examples 1-6 and Comparative Examples 1-3).
比較例６
板厚０．２５ｍｍのＮｂ−Ｔｉ−Ｓｕｌｃ鋼（再結晶鋼板）を原板とし、調質圧延の後、５％ＮａＯＨ水溶液による脱脂処理および５％硫酸水溶液による表面活性化処理を行った後、半光沢添加剤入Ｎｉメッキを行った。調質圧延および半光沢添加剤入Ｎｉメッキは、先の例（本発明例１〜６および比較例１〜３）と全く同一に行った。
Comparative Example 6
Nb-Ti-Sulc steel (recrystallized steel plate) having a thickness of 0.25 mm was used as a base plate, and after temper rolling, after degreasing treatment with 5% NaOH aqueous solution and surface activation treatment with 5% sulfuric acid aqueous solution, Ni plating with gloss additive was performed. Temper rolling and semi-gloss additive-added Ni plating were performed exactly as in the previous examples (Invention Examples 1-6 and Comparative Examples 1-3).
（性能評価方法）
（１） 耐食性；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、正極端子部外面を上に向けて、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。錆皆無を「○」、極軽微な錆（点状錆が５個まで）ありを「△」、錆ありを「×」と評価した。
（２） 摺動性；ＤＯＳ塗油（約０．１ｇ／ｍ2）材を幅３０ｍｍ＊長さ３００ｍｍにカットし、外面になる面を１０Ｒの蒲鉾型摺動子（超硬）、内面になる面を平面金型（超硬）で荷重２００ｋｇｆにて圧着し、２００ｍｍ／ｍｉｎの速度で１００ｍｍ引きぬき、外面側の摺動面のカジリ外観を目視した。Ｎ１０連続で行い、カジリ全くない場合を「○」、ごく軽微なカジリを「△」、カジリを「×」と評価した。
（３） 接触抵抗；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、６０℃９５％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にて正極端子部外面の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。
(Performance evaluation method)
(1) Corrosion resistance: Pressing a steel plate sample to produce a can for a normal LR06 type alkaline manganese battery, and conducting a salt spray test (JIS-Z-2371) for 3 hours with the positive electrode terminal portion outer surface facing up The appearance of red rust was visually observed. The evaluation was “◯” when there was no rust, “△” when there was very slight rust (up to 5 spot-like rusts), and “×” when there was rust.
(2) Sliding property: DOS oil (approx. 0.1 g / m 2 ) material is cut into a width of 30 mm * length of 300 mm, and the outer surface is a 10R vertical slider (super hard), and the inner surface The resulting surface was pressure-bonded with a flat metal mold (carbide) at a load of 200 kgf, pulled 100 mm at a speed of 200 mm / min, and the scouring appearance of the sliding surface on the outer surface side was visually observed. The test was carried out for N10 continuously, and the case where there was no galling was evaluated as “◯”, the very slight galling was evaluated as “Δ”, and the galling was evaluated as “×”.
(3) Contact resistance: A steel plate sample was pressed to produce a can for a normal LR06 type alkaline manganese battery, left at 60 ° C. and 95% RH for 20 days, and then an electrical contact simulator CRS-1 manufactured by Yamazaki Seiki Laboratory. The contact resistance of the outer surface of the positive electrode terminal portion was measured at a load of 100 g. 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”.
以上の評価結果を表１に示す。表１に示すように、本発明例では良好な耐食性、摺動性、接触抵抗が得られた。 The above evaluation results are shown in Table 1. As shown in Table 1, good corrosion resistance, slidability, and contact resistance were obtained in the inventive examples.
本発明の電池缶用Ｎｉメッキ鋼板は、耐食性、摺動性および接触抵抗に優れ、電池缶の耐食性、電池特性、表面摺動性を改善しうるものであるから、一次電池、二次電池等の電池缶に用いることができる。 The Ni-plated steel sheet for battery cans of the present invention is excellent in corrosion resistance, slidability and contact resistance, and can improve the corrosion resistance, battery characteristics and surface slidability of battery cans, so primary batteries, secondary batteries, etc. It can be used for battery cans.
Claims (3)
上記Ｆｅ−Ｎｉ拡散層、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層の付着量は、Ｎｉとして（Ｆｅ−Ｎｉ拡散層のＮｉ量、または、Ｆｅ−Ｎｉ拡散層とその上層の再結晶軟質化されたＮｉメッキ層の合計のＮｉ量）５〜４５ｇ／ｍ 2 であり、上記光沢添加剤または半光沢添加剤含有Ｎｉメッキ層の付着量が、０．５ｇ／ｍ 2 以上であり、かつ、その下層のＮｉ量（Ｆｅ−Ｎｉ拡散層のＮｉ量、または、Ｆｅ−Ｎｉ拡散層とその上層の再結晶軟質化されたＮｉメッキ層の合計のＮｉ量）以下で
あることを特徴とする電池缶用Ｎｉメッキ鋼板。 Fe-Ni diffusion layer or Fe-Ni diffusion layer on the surface corresponding to the outer surface of the battery can and Ni-plated layer that is recrystallized and softened on the upper layer, and further contains a gloss additive or semi-gloss additive It has a Ni plating layer, and its surface roughness Ra is 0.3 μm or more ,
The amount of adhesion of the Fe-Ni diffusion layer or the Fe-Ni diffusion layer and the Ni plating layer recrystallized and softened on the Fe-Ni diffusion layer is Ni (Fe amount of the Fe-Ni diffusion layer or Fe-Ni diffusion layer). And the total amount of Ni in the recrystallized and softened Ni plating layer on the upper layer) is 5 to 45 g / m 2 , and the adhesion amount of the Ni plating layer containing the gloss additive or the semi-gloss additive is 0.5 g / m 2. m 2 or more and lower Ni amount (Ni amount of Fe-Ni diffusion layer or total Ni amount of Fe-Ni diffusion layer and recrystallized / softened Ni plating layer) A Ni-plated steel sheet for battery cans, characterized in that
A battery can comprising the Ni-plated steel sheet according to claim 1 or 2 .
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120130076A (en) | 2010-01-08 | 2012-11-28 | 도요 고한 가부시키가이샤 | Ni-plated steel sheet with excellent pressability for battery can |
| CN103343367A (en) * | 2013-07-12 | 2013-10-09 | 深圳市中金高能电池材料有限公司 | Nickel-plated steel strip and preparation method thereof |
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| JP4612573B2 (en) * | 2006-03-24 | 2011-01-12 | 新日本製鐵株式会社 | Method for producing multilayer Ni diffusion plated steel sheet |
| JP4612572B2 (en) * | 2006-03-24 | 2011-01-12 | 新日本製鐵株式会社 | Manufacturing method of high purity Ni diffusion plated steel sheet |
| JP2008041527A (en) * | 2006-08-09 | 2008-02-21 | Matsushita Electric Ind Co Ltd | Battery can, and battery using it |
| JP5078482B2 (en) * | 2007-07-23 | 2012-11-21 | Ｆｄｋエナジー株式会社 | Sealed battery and battery can |
| JP4995140B2 (en) * | 2008-04-25 | 2012-08-08 | 新日本製鐵株式会社 | Ni-plated steel sheet for containers, container manufactured thereby, and method for manufacturing the same |
| CN102458701A (en) * | 2009-06-09 | 2012-05-16 | 东洋钢钣株式会社 | Nickel-plated steel sheet and process for producing battery can using the nickel-plated steel sheet |
| KR101244554B1 (en) | 2009-08-26 | 2013-03-18 | 도요 고한 가부시키가이샤 | Ni-plated steel sheet for battery can having excellent pressability |
| JP2011192559A (en) * | 2010-03-15 | 2011-09-29 | Fdk Energy Co Ltd | Battery can and alkaline battery |
| CN105177650A (en) * | 2015-09-10 | 2015-12-23 | 湖南东洋利德材料科技有限公司 | Nickel plating method of steel belts for steel battery shells |
| US20230407509A1 (en) * | 2020-12-03 | 2023-12-21 | Nippon Steel Corporation | Surface-treated steel sheet |
| WO2023210832A1 (en) * | 2022-04-29 | 2023-11-02 | 東洋鋼鈑株式会社 | Nickel-plated steel sheet and method for producing same |
| CN115787014B (en) * | 2022-11-30 | 2023-10-13 | 江苏东方九天新能源材料有限公司 | Surface treatment process of nickel-plated steel strip of battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120130076A (en) | 2010-01-08 | 2012-11-28 | 도요 고한 가부시키가이샤 | Ni-plated steel sheet with excellent pressability for battery can |
| CN103343367A (en) * | 2013-07-12 | 2013-10-09 | 深圳市中金高能电池材料有限公司 | Nickel-plated steel strip and preparation method thereof |
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