JPH09263994A - Battery can material excellent in deep drawability and its production - Google Patents
Battery can material excellent in deep drawability and its productionInfo
- Publication number
- JPH09263994A JPH09263994A JP8097791A JP9779196A JPH09263994A JP H09263994 A JPH09263994 A JP H09263994A JP 8097791 A JP8097791 A JP 8097791A JP 9779196 A JP9779196 A JP 9779196A JP H09263994 A JPH09263994 A JP H09263994A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- plating
- heating
- diffusion layer
- steel sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、深絞り加工性に優れ且
つ電池特性が向上する電池缶材料及びその製造方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery can material having excellent deep drawability and improved battery characteristics, and a method for producing the same.
【０００２】[0002]
【従来の技術】電池缶材料には、電気Ｎｉめっき鋼板
や、電気Ｎｉめっき後に加熱拡散処理を施しＮｉ−Ｆｅ
の拡散層を形成した材料が使用されている。他方、電池
ケースの成形加工は、従来の多段絞り加工からコスト低
減及び加工速度の上昇を狙ってＤＩ（ｄｒａｗｉｎｇ
ａｎｄ ｉｒｏｎｉｎｇ）加工法に移行しつつある。し
たがって、加工方法の変更に伴って、電池缶材料に対し
ても新たな材料特性が要求されるようになってきた。た
とえば、従来から使用されてきた電池缶材料ではＤＩ法
による厳しい加工に追従できず、正極端子となる凸部が
付いた缶胴を成形する際に凸部のコーナーが破断するこ
とがある。また、電気Ｎｉめっき鋼板では、めっき層が
パウダー状に剥落する欠点もある。更には、端子表面で
の接触電気抵抗が増大することも問題となる。これは、
電池が厳しい環境下で使用された場合、正負極端子部の
Ｎｉめっき層又はＮｉ−Ｆｅ拡散層の表面が腐食して接
触電気抵抗が増大することに原因がある。そのため、過
酷な環境下でも接触電気抵抗の経時変化が小さい材料が
望まれる。そこで、特開平６−１０８２８６号公報で
は、電池缶の内面側にＮｉめっきを施し、外面側にＳｎ
めっきを施した電池缶材料が紹介されている。また、Ｎ
ｉめっき後に拡散処理を行うとき、Ｎｉめっき層が軟質
化し、加工時にめっき層でのクラック発生が抑制される
ことが開示されている。2. Description of the Related Art A battery can material is an Ni-plated steel sheet or an Ni-Fe sheet which has been subjected to a heat diffusion treatment after the Ni plating.
The material forming the diffusion layer is used. On the other hand, the battery case is formed by DI (drawing) in order to reduce the cost and increase the processing speed from the conventional multi-stage drawing.
and ironing) processing method. Therefore, with the change in the processing method, new material characteristics have come to be required also for the battery can material. For example, conventionally used battery can materials cannot follow severe processing by the DI method, and the corners of the convex parts may be broken when forming a can body with a convex part that serves as a positive electrode terminal. In addition, the electric Ni-plated steel sheet has a drawback that the plating layer is peeled off in powder form. Another problem is that the contact electric resistance on the surface of the terminal increases. this is,
When the battery is used in a severe environment, the surface of the Ni plating layer or the Ni—Fe diffusion layer in the positive and negative electrode terminal portions corrodes, which increases the contact electric resistance. Therefore, a material whose contact electric resistance changes little with time even in a harsh environment is desired. Therefore, in Japanese Patent Laid-Open No. 6-108286, Ni plating is applied to the inner surface side of the battery can and Sn is applied to the outer surface side.
Plated battery can materials are introduced. Also, N
It is disclosed that when a diffusion treatment is performed after i-plating, the Ni plating layer is softened and cracking in the plating layer is suppressed during processing.
【０００３】[0003]
【発明が解決しようとする課題】しかし、特開平６−１
０８２８６号公報の電池缶材料は、電気Ｎｉめっき→加
熱拡散処理→電気Ｓｎめっきの工程を経て製造される。
すなわち、加熱拡散処理を挟んで二度のめっき工程が必
要とされ、工業的規模での製造を考慮すると製造コスト
が高くなる欠点がある。本発明は、このような問題を解
消すべく案出されたものであり、鋼板の両面にＦｅ−Ｎ
ｉ拡散層を形成すると共に、電池缶外面に相当する面上
にＮｉ−Ｃｕ拡散層を形成することにより、安価に製造
でき、電池特性及び深絞り加工性が優れた電池缶材料を
提供することを目的とする。However, Japanese Patent Application Laid-Open No.
The battery can material disclosed in Japanese Patent No. 08286 is manufactured through the steps of electric Ni plating → heat diffusion treatment → electric Sn plating.
That is, two plating steps are required with the heat diffusion process interposed therebetween, which is disadvantageous in that the manufacturing cost becomes high in consideration of manufacturing on an industrial scale. The present invention was devised to solve such a problem, and Fe-N is formed on both sides of the steel sheet.
To provide a battery can material that can be manufactured at low cost and has excellent battery characteristics and deep drawing workability by forming an i diffusion layer and a Ni-Cu diffusion layer on the surface corresponding to the outer surface of the battery can. With the goal.
【０００４】[0004]
【課題を解決するための手段】本発明の電池缶材料は、
その目的を達成するため、冷延鋼板を下地とし、その両
面に形成されたＮｉ−Ｆｅの拡散層と、電池缶外面に相
当する面上に形成されたＣｕ：５〜４０重量％を含むＮ
ｉ−Ｃｕ拡散層とを有することを特徴とする。この電池
缶材料は、冷延鋼板の両面にＮｉめっきを施し、更に電
池缶外面に相当する側でＮｉめっき層の上にＣｕめっき
を施した後、連続焼鈍又は箱型焼鈍で加熱拡散処理する
ことによって製造される。連続焼鈍では、７００〜９０
０℃に３０秒〜２分間加熱する条件が採用される。箱型
焼鈍では、５００〜８００℃に５〜８時間加熱する条件
が採用される。Means for Solving the Problems The battery can material of the present invention is
In order to achieve the object, a cold-rolled steel sheet is used as a base, Ni-Fe diffusion layers formed on both surfaces thereof, and Cu containing 5 to 40% by weight of Cu formed on the surface corresponding to the outer surface of the battery can.
and an i-Cu diffusion layer. This battery can material is plated with Ni on both sides of a cold-rolled steel plate, and is further plated with Cu on the Ni plating layer on the side corresponding to the outer surface of the battery can, and then subjected to heat diffusion treatment by continuous annealing or box-type annealing. Manufactured by 700 to 90 in continuous annealing
The condition of heating to 0 ° C. for 30 seconds to 2 minutes is adopted. In the box-type annealing, conditions of heating at 500 to 800 ° C. for 5 to 8 hours are adopted.
【０００５】[0005]
【実施の形態】本発明の電池缶材料は、たとえば冷延
後、電解洗浄，焼鈍，調質圧延した低炭素Ａｌキルド鋼
板の両面に膜厚１〜３μｍの電気Ｎｉめっきを施し、更
に電池缶外面に相当する面に膜厚０．０５〜０．５μ
ｍ，好ましくは０．１〜０．３μｍの電気Ｃｕめっきを
施す。次いで、めっき後の鋼板を加熱拡散処理すること
により、両面にＮｉ−Ｆｅ拡散層を形成させ、更に電池
缶外面に相当する面にＣｕ含有量が５〜４０重量％のＮ
ｉ−Ｃｕ拡散層を形成させる。電気Ｎｉめっきには、一
般的に知られているワット浴，スルファミン浴，塩化物
浴等の無光沢Ｎｉめっき浴等が使用される、Ｎｉめっき
層の膜厚は、特に規制されるものではないが、電池缶と
しての用途では１〜３μｍの厚みが好ましい。電気Ｃｕ
めっきには、シアン化銅めっき浴，ピロリン酸銅めっき
浴，硫酸銅めっき浴等が使用される。電気Ｃｕめっき層
は、０．０５〜０．５μｍ，好ましくは０．１〜０．３
μｍの膜厚で形成される。Ｃｕめっき層の膜厚が０．０
５μｍ未満であると、加熱処理後のＮｉ−Ｃｕ拡散層の
Ｃｕ含有量が５重量％未満となり、良好な深絞り加工性
が得られない。逆に０．５μｍを超える膜厚では、Ｃｕ
含有量が４０重量％を超え、過酷な環境下においては時
間経過に伴って接触電気抵抗が大きく低下する。BEST MODE FOR CARRYING OUT THE INVENTION The battery can material of the present invention is, for example, after cold rolling, electrolytically cleaned, annealed, temper-rolled, and low carbon Al killed steel sheet is electroplated with Ni to a thickness of 1 to 3 μm. 0.05-0.5μ film thickness on the surface corresponding to the outer surface
m, preferably 0.1-0.3 μm electro-Cu plating. Then, the plated steel sheet is subjected to a heat diffusion treatment to form Ni-Fe diffusion layers on both surfaces, and further, a Cu content of 5 to 40% by weight on the surface corresponding to the outer surface of the battery can.
An i-Cu diffusion layer is formed. A commonly known Watt bath, sulfamine bath, chloride bath, or other matte Ni plating bath is used for the electric Ni plating. The thickness of the Ni plating layer is not particularly limited. However, a thickness of 1 to 3 μm is preferable for use as a battery can. Electric Cu
For the plating, a copper cyanide plating bath, a copper pyrophosphate plating bath, a copper sulfate plating bath, or the like is used. The electric Cu plating layer has a thickness of 0.05 to 0.5 μm, preferably 0.1 to 0.3.
It is formed with a film thickness of μm. Cu plating layer thickness is 0.0
When it is less than 5 μm, the Cu content of the Ni—Cu diffusion layer after the heat treatment becomes less than 5% by weight, and good deep drawability cannot be obtained. On the contrary, when the film thickness exceeds 0.5 μm, Cu
When the content exceeds 40% by weight, the contact electric resistance significantly decreases with the passage of time in a severe environment.
【０００６】電気Ｎｉめっき及び電気Ｃｕめっきを工業
的規模で行う場合、電気Ｎｉめっきを施した後、最終の
電解セルで電気Ｃｕめっきを施す方式が採用できる。こ
れにより、１ラインでの製造が可能となるので、電気Ｎ
ｉめっきと電気Ｓｎめっきとの間に加熱拡散工程を挟ん
だ方式に比較して製造工程が大幅に簡略化されたものと
なる。めっき後の鋼板を加熱拡散処理するとき、鋼板両
面にＮｉ−Ｆｅ拡散層が形成され、電池缶外面に相当す
る面上にＮｉ−Ｃｕ拡散層が形成される。加熱処理に
は、箱型焼鈍又は連続焼鈍の何れをも採用できる。加熱
時のガス雰囲気は、非酸化性又は還元性のガス雰囲気が
好ましい。箱型焼鈍の加熱条件は、加熱温度５００〜８
００℃，均熱時間５〜８時間が好適である。５００℃に
達しない加熱温度では、Ｎｉ−Ｃｕ拡散層の形成が不十
分となり、良好な深絞り加工性及び接触電気抵抗が得ら
れない。逆に８００℃を超える加熱温度では、めっき原
板であるＡｌキルド鋼板の結晶粒が粗大化し、結果とし
てプレス成形時に缶の表面に肌荒れが生じる。加熱時間
については、５時間未満ではＮｉ−Ｃｕ拡散層の形成が
不十分になる。他方、８時間を超えると電池缶材料とし
ての優れた特性に変化がみられず、長時間加熱に起因し
た生産性の低下及び熱損失が大きくなる。When performing the electric Ni plating and the electric Cu plating on an industrial scale, it is possible to employ a method in which after performing the electric Ni plating, the electric Cu plating is performed in the final electrolytic cell. As a result, it is possible to manufacture on one line.
The manufacturing process is greatly simplified as compared with the method in which the heat diffusion process is interposed between the i plating and the electric Sn plating. When the plated steel sheet is subjected to heat diffusion treatment, Ni-Fe diffusion layers are formed on both surfaces of the steel sheet, and a Ni-Cu diffusion layer is formed on a surface corresponding to the outer surface of the battery can. For the heat treatment, either box-type annealing or continuous annealing can be adopted. The gas atmosphere during heating is preferably a non-oxidizing or reducing gas atmosphere. The heating condition of the box-type annealing is a heating temperature of 500 to 8
It is preferable that the temperature is 00 ° C. and the soaking time is 5 to 8 hours. If the heating temperature does not reach 500 ° C., the formation of the Ni—Cu diffusion layer becomes insufficient, and good deep drawability and contact electric resistance cannot be obtained. On the contrary, at a heating temperature of higher than 800 ° C., the crystal grains of the Al-killed steel plate, which is the original plating plate, become coarse, and as a result, the surface of the can is roughened during press forming. When the heating time is less than 5 hours, the formation of the Ni-Cu diffusion layer becomes insufficient. On the other hand, if it exceeds 8 hours, the excellent properties as a battery can material are not changed, and the productivity is reduced and the heat loss is increased due to long-time heating.
【０００７】連続焼鈍の加熱条件は、加熱温度７００〜
９００℃，均熱時間３０秒〜２分が好適である。７００
℃に達しない加熱温度では、Ｎｉ−Ｃｕ拡散層の形成が
不十分となる。逆に９００℃を超える加熱温度では、め
っき原板であるＡｌキルド鋼板の結晶粒が粗大化し、結
果としてプレス成形時に缶の表面に肌荒れが生じる。ま
た、２分を超える加熱は、電池缶材料としての優れた特
性に変化がみられず、長時間加熱に起因した生産性の低
下及び熱損失が大きくなる。加熱拡散処理によって形成
されたＮｉ−Ｆｅ拡散層は、軟質で加工性に優れるた
め、缶内面側ではプレス成形加工時にＮｉ−Ｆｅ拡散層
のクラック発生が非常に少なく、クラックに起因した原
板（Ｆｅ）の露出が抑制される。したがって、アルカリ
マンガン電池等の電解液として使用されるＫＯＨ溶液に
対して鋼板の腐食及びＦｅの溶出等を防止し、良好な電
池特性が維持される。Ｎｉ−Ｃｕ拡散層は、軟質化して
金型との摺動抵抗を低下し、深絞り加工時の滑り込み性
を改善する作用を呈するものと推察される。良好な深絞
り加工性を得るためには、５重量％以上のＣｕ含有量が
必要である。しかし、４０重量％を超えるＣｕ含有量で
は、接触電気抵抗の経時劣化が大きくなる。これは、Ｎ
ｉ−Ｃｕ拡散層の表面が腐食・変色することに起因する
ものと推察される。したがって、優れた深絞り加工性及
び経時変化の小さい接触電気抵抗を得るためには、Ｎｉ
−Ｃｕ拡散層中のＣｕ含有量を５〜４０重量％の範囲に
することが必要とされる。加熱処理後の鋼板は、圧延率
１〜２％の調質圧延が施される。調質圧延では、鋼板表
面に光沢を付与するためブライトロールを使用すること
が好ましい。The heating conditions for continuous annealing are as follows:
A temperature of 900 ° C. and a soaking time of 30 seconds to 2 minutes are preferable. 700
If the heating temperature does not reach ℃, the formation of the Ni-Cu diffusion layer becomes insufficient. On the contrary, at a heating temperature higher than 900 ° C., the crystal grains of the Al-killed steel plate, which is the plating base plate, become coarse, and as a result, the surface of the can is roughened during press forming. Further, if the heating is performed for more than 2 minutes, the excellent properties as a battery can material are not changed, and the productivity is reduced and the heat loss is increased due to the long-time heating. Since the Ni-Fe diffusion layer formed by the heat diffusion treatment is soft and excellent in workability, cracks in the Ni-Fe diffusion layer during the press forming process on the inner surface of the can are very small, and the original plate (Fe ) Exposure is suppressed. Therefore, corrosion of the steel sheet and elution of Fe are prevented with respect to the KOH solution used as the electrolytic solution of the alkaline manganese battery or the like, and good battery characteristics are maintained. It is presumed that the Ni-Cu diffusion layer is softened to lower the sliding resistance with the die, and exhibits the effect of improving the slip-in property during deep drawing. A Cu content of 5% by weight or more is necessary to obtain good deep drawability. However, when the Cu content exceeds 40% by weight, the contact electric resistance deteriorates with time. This is N
It is inferred that the surface of the i-Cu diffusion layer is corroded and discolored. Therefore, in order to obtain excellent deep drawing workability and contact electric resistance with little change over time, Ni
-The Cu content in the Cu diffusion layer is required to be in the range of 5 to 40% by weight. The heat-treated steel sheet is temper-rolled at a rolling rate of 1 to 2%. In temper rolling, it is preferable to use a bright roll in order to impart gloss to the surface of the steel sheet.
【０００８】[0008]
実施例１：Ｃ：０．０２６重量％，Ｓｉ：０．０７重量
％，Ｍｎ：０．２１重量％，Ｐ：０．００９重量％，
Ｓ：０．００８重量％，酸可溶Ａｌ：０．０３５重量
％，Ｎ：０．００１６重量％の組成を持つ板厚０．２５
ｍｍのＡｌキルド鋼板をめっき原板として使用した。こ
のめっき原板を、浴温６０℃，オルトケイ酸ソーダ５０
ｇ／ｌのアルカリ電解浴に浸漬して０．５ｋＡ／ｍ2 ×
１０秒で陰極電解することにより電解脱脂し、浴温３０
℃，硫酸５０ｇ／ｌの硫酸浴に１０秒間浸漬して硫酸酸
洗した。次いで、以下のワット浴で鋼板表面に膜厚３μ
ｍの電気Ｎｉめっきを施した。 Example 1: C: 0.026% by weight, Si: 0.07% by weight, Mn: 0.21% by weight, P: 0.009% by weight,
Plate thickness 0.25 having a composition of S: 0.008% by weight, acid-soluble Al: 0.035% by weight, N: 0.0016% by weight
An Al killed steel plate of mm was used as a plating original plate. This plating base plate is treated with a bath temperature of 60 ° C. and sodium orthosilicate 50
0.5kA / m 2 × by immersing in an alkaline electrolysis bath of g / l
Electrolyte degreasing by cathodic electrolysis in 10 seconds, bath temperature 30
It was immersed in a sulfuric acid bath of 50 g / l of sulfuric acid at 10 ° C. for 10 seconds for sulfuric acid pickling. Then, in the following watt bath, the film thickness of 3μ on the steel plate surface
m electrical Ni plating was applied.
【０００９】電気Ｎｉめっきした鋼板を水洗した後、シ
アン化銅浴を使用して膜厚０．０２〜１μｍの電気Ｃｕ
めっき層を片面に形成した。 電気Ｃｕめっき 浴組成：シアン化銅 ３０ｇ／ｌ シアン化ナトリウム ４５ｇ／ｌ 浴温度：３０℃， ｐＨ：１１．４〜１２．０ 電流密度：０．４ｋＡ／ｍ2 次いで、連続焼鈍法により２％Ｈ2 −Ｎ2 ガス雰囲気中
で加熱温度７２０℃，加熱時間１分の加熱拡散処理を施
し、両面にＮｉ−Ｆｅ拡散層を、片面のＮｉ−Ｆｅ拡散
層の上にＮｉ−Ｃｕ拡散層を形成した。拡散処理後、圧
延率１％の調質圧延を施した。以上の条件で得られた各
試料について、深絞り加工性及び促進劣化試験後の接触
電気抵抗を調査した。After washing an electric Ni-plated steel plate with water, an electric Cu having a film thickness of 0.02 to 1 μm is formed using a copper cyanide bath.
The plating layer was formed on one side. Electro-Cu plating Bath composition: Copper cyanide 30 g / l Sodium cyanide 45 g / l Bath temperature: 30 ° C., pH: 11.4-12.0 Current density: 0.4 kA / m 2 Then, 2% by continuous annealing method A heat diffusion process was performed in a H 2 —N 2 gas atmosphere at a heating temperature of 720 ° C. for a heating time of 1 minute to form a Ni—Fe diffusion layer on both sides and a Ni—Cu diffusion layer on one side of the Ni—Fe diffusion layer. Formed. After the diffusion treatment, temper rolling with a rolling ratio of 1% was performed. For each sample obtained under the above conditions, the deep drawability and the contact electric resistance after the accelerated deterioration test were investigated.
【００１０】深絞り加工性試験では、Ｎｉ−Ｃｕ拡散層
側が円筒の外側となるようにブランク径９３ｍｍ，パン
チ径４０ｍｍ，しわ押え５ｋＮの条件で円筒絞りを行
い、Ｏ．Ｄ．Ｒ．（外径比）を算出し、加工性を評価し
た。促進劣化試験では、温度５０℃，相対湿度７０％の
恒温恒湿槽内に試験片を１か月間放置した。接触電気抵
抗は、株式会社山崎精機研究所製の接触電気抵抗分布測
定器を使用し、印加電流１０ｍＡ，接触荷重１００ｇの
条件下で測定した。現行電池缶材料であるＮｉめっき材
では、試験前の接触電気抵抗が５ｍΩ以下であったが、
試験後には２０〜３０ｍΩとなった。そこで、試験後の
接触電気抵抗が１０ｍΩ以下のものを○，１１〜５０ｍ
Ωのものを△，５１ｍΩ以上を×として三段階評価し
た。図１の試験結果にみられるように、深絞り加工性
は、Ｎｉ−Ｃｕ拡散層中のＣｕ含有量が５重量％未満で
はＮｉめっき材と同レベルであったが、５重量％以上の
Ｃｕ含有量ではＮｉめっき材よりも優れていることが判
る。また、Ｎｉ−Ｃｕ拡散層中のＣｕ含有量が５〜４０
重量％の範囲にあるとき、優れた接触電気抵抗が得られ
ることが判る。In the deep drawing workability test, cylindrical drawing was performed under the conditions of a blank diameter of 93 mm, a punch diameter of 40 mm, and a crease presser of 5 kN so that the Ni-Cu diffusion layer side was the outside of the cylinder. D. R. (Outer diameter ratio) was calculated and workability was evaluated. In the accelerated deterioration test, the test piece was left for 1 month in a thermo-hygrostat at a temperature of 50 ° C. and a relative humidity of 70%. The contact electric resistance was measured under the conditions of an applied current of 10 mA and a contact load of 100 g using a contact electric resistance distribution measuring instrument manufactured by Yamazaki Seiki Co., Ltd. The Ni plating material, which is the current battery can material, had a contact electric resistance of 5 mΩ or less before the test.
It became 20 to 30 mΩ after the test. Therefore, if the contact electric resistance after the test is 10 mΩ or less, ○, 11 to 50 m
Ω was evaluated as Δ, and 51 mΩ or more was evaluated as x, and three-stage evaluation was performed. As can be seen from the test results of FIG. 1, the deep drawability was at the same level as that of the Ni-plated material when the Cu content in the Ni—Cu diffusion layer was less than 5% by weight, but was 5% by weight or more. It can be seen that the content is superior to the Ni plated material. Further, the Cu content in the Ni—Cu diffusion layer is 5 to 40.
It can be seen that excellent contact electric resistance is obtained in the range of weight%.
【００１１】実施例２：実施例１と同じめっき原板を前
処理し、スルファミン酸浴で膜厚１〜３μｍの電気Ｎｉ
めっき層をめっき原板の両面に形成した。 電気Ｎｉめっき 浴組成：スルファミン酸ニッケル ３２０ｇ／ｌ 硼酸 ３０ｇ／ｌ 臭化ニッケル １０ｇ／ｌ 浴温度：４０℃， ｐＨ：３．５， 電流密度：１ｋＡ／ｍ2 電気Ｎｉめっきした鋼板を水洗した後、シアン化銅浴を
使用して膜厚０．０２〜１μｍの電気Ｃｕめっき層を片
面に形成した。 電気Ｃｕめっき 浴組成：硫酸銅 ２５０ｇ／ｌ 硫酸 ５５ｇ／ｌ 浴温度：３０℃， 電流密度：０．５ｋＡ／ｍ2 Example 2: The same plating base plate as in Example 1 was pretreated, and an electric Ni having a film thickness of 1 to 3 μm was formed in a sulfamic acid bath.
Plating layers were formed on both sides of the original plating plate. Electro Ni plating bath composition: Nickel sulfamate 320 g / l Boric acid 30 g / l Nickel bromide 10 g / l Bath temperature: 40 ° C., pH: 3.5, Current density: 1 kA / m 2 After washing the electro Ni plated steel plate with water Then, an electric Cu plating layer having a film thickness of 0.02 to 1 μm was formed on one surface using a copper cyanide bath. Electro Cu plating Bath composition: Copper sulfate 250 g / l Sulfuric acid 55 g / l Bath temperature: 30 ° C. Current density: 0.5 kA / m 2
【００１２】得られためっき鋼板を、連続焼鈍法により
加熱拡散処理した。連続焼鈍では、２％Ｈ2 −Ｎ2 雰囲
気中で加熱温度７００〜９００℃，加熱時間３０秒〜２
分の範囲で加熱条件を変化させた。次いで、圧延率１％
の調質圧延を施した。得られた各試料について、深絞り
加工性，促進劣化試験後の接触電気抵抗及び耐パウダリ
ング性を調査した。なお、比較材として、膜厚３μｍの
Ｎｉめっきまま材（Ｎo.１５），膜厚３μｍのＮｉめっ
き材を加熱温度７２０℃，加熱時間１分で加熱拡散処理
したもの（Ｎo.１６）を使用した。深絞り加工性は、実
施例１と同じ試験方法で調査し、現行の電池缶材料であ
るＮｉめっき材のＯ．Ｄ．Ｒ．値０．９５と比較し、
０．９０以下を○，０．９１〜０．９５を△，０．９６
以上を×として評価した。促進劣化試験後の接触電気抵
抗は、実施例１と同様に評価した。また、耐パウダリン
グ性は、ビード付きＵ曲げ加工をしわ押え力２．５ｋ
Ｎ，成形高さ５０ｍｍの条件下でＮｉ−Ｃｕ拡散層側が
成形面の外側になるように加工し、図２に示す試験部位
でパウダーの発生量を調査した。The plated steel sheet thus obtained was subjected to a heat diffusion treatment by a continuous annealing method. In the continuous annealing, the heating temperature is 700 to 900 ° C. and the heating time is 30 seconds to 2 in a 2% H 2 —N 2 atmosphere.
The heating conditions were changed within the range of minutes. Then 1% rolling rate
Temper rolling. For each of the obtained samples, deep drawing workability, contact electric resistance after accelerated deterioration test, and powdering resistance were investigated. As a comparative material, a Ni-plated material with a film thickness of 3 μm (No. 15) and a Ni-plated material with a film thickness of 3 μm subjected to heat diffusion treatment at a heating temperature of 720 ° C. for a heating time of 1 minute (No. 16) were used. did. The deep drawing workability was investigated by the same test method as in Example 1, and the O.V. D. R. Compared to the value 0.95,
0.90 or less is ○, 0.91 to 0.95 is △, 0.96
The above was evaluated as x. The contact electric resistance after the accelerated deterioration test was evaluated in the same manner as in Example 1. Also, the powdering resistance is U-bending with beads, and the wrinkle holding force is 2.5k.
Under the conditions of N and molding height of 50 mm, the Ni-Cu diffusion layer side was processed so that the side was outside the molding surface, and the amount of powder generated was examined at the test site shown in FIG.
【００１３】調査結果を示す表１にみられるように、本
発明に従った試験片Ｎo.１〜９は、何れも全ての試験で
良好な結果を示した。しかし、Ｎｉ−Ｃｕ拡散層のＣｕ
含有量が低い試験番号１０，１２やＮｉ−Ｃｕ拡散層の
ない試験番号１５，１６では、深絞り加工性が劣ってい
た。また、促進劣化試験後の接触電気抵抗も増加してい
た。他方、Ｃｕ含有量が過剰な試験番号１１，１３，１
４では、促進劣化試験後に接触電気抵抗が大きく増加し
ていた。As can be seen from Table 1 showing the investigation results, the test pieces Nos. 1 to 9 according to the present invention all showed good results in all the tests. However, Cu in the Ni-Cu diffusion layer
In the test numbers 10 and 12 having a low content and the test numbers 15 and 16 having no Ni—Cu diffusion layer, the deep drawing workability was inferior. Further, the contact electric resistance after the accelerated deterioration test was also increased. On the other hand, test numbers 11, 13, 1 with excessive Cu content
In No. 4, the contact electric resistance increased significantly after the accelerated deterioration test.
【００１４】 [0014]
【００１５】実施例３：実施例１と同じめっき原板を使
用し、実施例２と同様にめっき原板の両面に電気Ｎｉめ
っきを施した後、片面上に電気Ｃｕめっき層を形成し
た。そして、１０％Ｈ2 −Ｎ2 雰囲気下の箱型焼鈍法で
拡散熱処理を施した。このとき、加熱温度５００〜８０
０℃，加熱時間５〜８時間の範囲で加熱条件を変化させ
た。次いで、圧延率１％で調質圧延した。得られた各試
料について、実施例２と同様に深絞り加工性，促進劣化
試験後の接触電気抵抗及び耐パウダリング性を調査し
た。なお、比較材として、膜厚３μｍのＮｉめっきまま
材（Ｎo.３１），膜厚３μｍのＮｉめっき材を加熱温度
６００℃，加熱時間６時間で加熱拡散処理したもの（Ｎ
o.３２）を使用した。調査結果を示す表２にみられるよ
うに、本発明に従った試験片Ｎo.１７〜２５は、何れも
全ての試験で良好な結果を示した。しかし、Ｎｉ−Ｃｕ
拡散層のＣｕ含有量が低い試験番号２６，２８やＮｉ−
Ｃｕ拡散層のない試験番号３１，３２では、深絞り加工
性が劣っていた。また、促進劣化試験後の接触電気抵抗
も増加していた。他方、Ｃｕ含有量が過剰な試験番号２
７，２９，３０では、促進劣化試験後に接触電気抵抗が
大きく増加していた。なお、加熱条件によっては、Ｎｉ
−Ｃｕ拡散層中に１０重量％程度までＦｅが拡散する場
合があるが、この程度のＦｅ含有量では深絞り加工性，
接触電気抵抗及び耐パウダリング性に悪影響がみられな
かった。Example 3: The same plating base plate as in Example 1 was used, and after electroplating Ni on both sides of the plating base plate in the same manner as in Example 2, an electric Cu plating layer was formed on one side. Then, diffusion heat treatment was performed by a box annealing method in a 10% H 2 —N 2 atmosphere. At this time, the heating temperature is 500 to 80
The heating conditions were changed within the range of 0 ° C. and the heating time of 5 to 8 hours. Then, temper rolling was performed at a rolling rate of 1%. For each of the obtained samples, the deep drawing workability, the contact electric resistance after the accelerated deterioration test, and the powdering resistance were examined in the same manner as in Example 2. As comparative materials, a Ni-plated material having a film thickness of 3 μm (No. 31) and a Ni-plated material having a film thickness of 3 μm were heated and diffused at a heating temperature of 600 ° C. for a heating time of 6 hours (N.
o.32) was used. As shown in Table 2 showing the investigation results, the test pieces Nos. 17 to 25 according to the present invention all showed good results in all the tests. However, Ni-Cu
Test No. 26, 28 or Ni- with low Cu content in the diffusion layer
In the test numbers 31 and 32 having no Cu diffusion layer, the deep drawability was inferior. Further, the contact electric resistance after the accelerated deterioration test was also increased. On the other hand, test number 2 with excessive Cu content
In Nos. 7, 29 and 30, the contact electric resistance increased significantly after the accelerated deterioration test. Depending on the heating conditions, Ni
-Fe may diffuse up to about 10% by weight in the Cu diffusion layer. However, with such an Fe content, deep drawing workability,
No adverse effects were observed on the contact electric resistance and the powdering resistance.
【００１６】 [0016]
【００１７】[0017]
【発明の効果】以上に説明したように、本発明の電池缶
材料は、電池缶外面に相当する面にＮｉ−Ｃｕ拡散層を
形成しているので、Ｎｉめっき材の現行電池缶材料に比
較して接触電気抵抗の経時変化が小さく、深絞り加工性
も優れている。そのため、コスト低減や加工速度の上昇
を狙ったＤＩ加工に適した材料として使用される。As described above, since the battery can material of the present invention has the Ni-Cu diffusion layer formed on the surface corresponding to the outer surface of the battery can, it is compared with the current battery can material of Ni plating material. As a result, the change in contact electric resistance with time is small and the deep drawability is excellent. Therefore, it is used as a material suitable for DI processing aiming at cost reduction and increase in processing speed.
【図１】 Ｎｉ−Ｃｕ拡散層のＣｕ含有量が深絞り加工
性及び促進劣化試験後の接触電気抵抗に及ぼす影響FIG. 1 Influence of Cu content of Ni-Cu diffusion layer on deep drawability and contact electric resistance after accelerated deterioration test.
【図２】 パウダー発生量を求めた試験部位[Fig. 2] Test site for powder generation
フロントページの続き (72)発明者 清水 剛 大阪府堺市石津西町５番地 日新製鋼株式 会社技術研究所内Front page continued (72) Inventor Tsuyoshi Shimizu 5 Ishizu Nishimachi, Sakai City, Osaka Prefecture Nisshin Steel Co., Ltd. Technical Research Institute
Claims (3)
れたＮｉ−Ｆｅの拡散層と、電池缶外面に相当する面上
に形成されたＣｕ：５〜４０重量％を含むＮｉ−Ｃｕ拡
散層とを有する深絞り加工性に優れ且つ接触電気抵抗の
経時変化が小さい電池缶材料。1. A Ni-Cu diffusion layer formed on both surfaces of a cold-rolled steel sheet as a base, and Ni-Cu containing Cu: 5 to 40 wt% formed on a surface corresponding to the outer surface of a battery can. A battery can material having a diffusion layer, which is excellent in deep drawability and has a small change in contact electric resistance with time.
に電池缶外面に相当する側でＮｉめっき層の上に膜厚
０．０５〜０．５μｍのＣｕめっきを施した後、７００
〜９００℃に３０秒〜２分間加熱する連続焼鈍を施す請
求項１記載の深絞り加工性に優れた電池缶材料の製造方
法。2. A cold-rolled steel sheet is plated with Ni on both sides, and further, Cu is plated with a thickness of 0.05 to 0.5 μm on the Ni plated layer on the side corresponding to the outer surface of the battery can.
The method for producing a battery can material excellent in deep drawing workability according to claim 1, wherein continuous annealing is performed by heating to ~ 900 ° C for 30 seconds to 2 minutes.
に電池缶外面に相当する側でＮｉめっき層の上に膜厚
０．０５〜０．５μｍのＣｕめっきを施した後、５００
〜８００℃に５〜８時間加熱する箱型焼鈍を施す請求項
１記載の深絞り加工性に優れた電池缶材料の製造方法。3. A cold-rolled steel sheet is plated with Ni on both sides, and further with Cu plating having a thickness of 0.05 to 0.5 μm on the Ni plating layer on the side corresponding to the outer surface of the battery can, and then 500.
The method for producing a battery can material excellent in deep drawability according to claim 1, wherein box annealing is performed by heating to ~ 800 ° C for 5 to 8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09779196A JP3439912B2 (en) | 1996-03-26 | 1996-03-26 | Battery can material excellent in deep drawability and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09779196A JP3439912B2 (en) | 1996-03-26 | 1996-03-26 | Battery can material excellent in deep drawability and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09263994A true JPH09263994A (en) | 1997-10-07 |
| JP3439912B2 JP3439912B2 (en) | 2003-08-25 |
Family
ID=14201643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09779196A Expired - Fee Related JP3439912B2 (en) | 1996-03-26 | 1996-03-26 | Battery can material excellent in deep drawability and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3439912B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11315346A (en) * | 1998-05-06 | 1999-11-16 | Nippon Steel Corp | Steel sheet for deep drawn can, excellent in immunity to earing, and its production |
| WO2006057788A1 (en) * | 2004-11-26 | 2006-06-01 | The Gillette Company | Zinc/air cell |
| WO2008044763A1 (en) * | 2006-10-13 | 2008-04-17 | Kyoritsu Chemical & Co., Ltd. | Tab lead material and process for producing the same |
| US7507297B2 (en) | 2002-05-20 | 2009-03-24 | Panasonic Corporation | Cleaning method and cleaning apparatus |
| WO2010113502A1 (en) | 2009-03-31 | 2010-10-07 | 新日本製鐵株式会社 | Material for metallic outer case for secondary battery utilizing non-aqueous electrolyte, metallic outer case, secondary battery, and process for production of material for metallic outer case |
| JP2010257927A (en) * | 2009-03-31 | 2010-11-11 | Nippon Steel Corp | Metal outer package case material for lithium ion battery with little voltage drop by metal elution, metal outer package case, and lithium ion battery |
| WO2013047514A1 (en) * | 2011-09-30 | 2013-04-04 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
| JP2017122281A (en) * | 2011-06-30 | 2017-07-13 | 東洋鋼鈑株式会社 | Production method of surface treatment steel, and production method of battery can |
-
1996
- 1996-03-26 JP JP09779196A patent/JP3439912B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11315346A (en) * | 1998-05-06 | 1999-11-16 | Nippon Steel Corp | Steel sheet for deep drawn can, excellent in immunity to earing, and its production |
| US7507297B2 (en) | 2002-05-20 | 2009-03-24 | Panasonic Corporation | Cleaning method and cleaning apparatus |
| WO2006057788A1 (en) * | 2004-11-26 | 2006-06-01 | The Gillette Company | Zinc/air cell |
| WO2008044763A1 (en) * | 2006-10-13 | 2008-04-17 | Kyoritsu Chemical & Co., Ltd. | Tab lead material and process for producing the same |
| WO2010113502A1 (en) | 2009-03-31 | 2010-10-07 | 新日本製鐵株式会社 | Material for metallic outer case for secondary battery utilizing non-aqueous electrolyte, metallic outer case, secondary battery, and process for production of material for metallic outer case |
| JP2010257927A (en) * | 2009-03-31 | 2010-11-11 | Nippon Steel Corp | Metal outer package case material for lithium ion battery with little voltage drop by metal elution, metal outer package case, and lithium ion battery |
| JP2017122281A (en) * | 2011-06-30 | 2017-07-13 | 東洋鋼鈑株式会社 | Production method of surface treatment steel, and production method of battery can |
| WO2013047514A1 (en) * | 2011-09-30 | 2013-04-04 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3439912B2 (en) | 2003-08-25 |
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