JP3631143B2 - Battery case and surface-treated steel sheet for battery case - Google Patents
Battery case and surface-treated steel sheet for battery case Download PDFInfo
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- JP3631143B2 JP3631143B2 JP2000614519A JP2000614519A JP3631143B2 JP 3631143 B2 JP3631143 B2 JP 3631143B2 JP 2000614519 A JP2000614519 A JP 2000614519A JP 2000614519 A JP2000614519 A JP 2000614519A JP 3631143 B2 JP3631143 B2 JP 3631143B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/545—Terminals formed by the casing of the cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
- H01M50/126—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers
- H01M50/128—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers with two or more layers of only inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/131—Primary casings, jackets or wrappings of a single cell or a single battery characterised by physical properties, e.g. gas-permeability or size
- H01M50/133—Thickness
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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
Description
技術分野
本発明は、アルカリ液を封入する容器、より詳しくはアルカリマンガン電池やニッケル−カドミウム電池などの電池外装ケース、及び、同ケースの作製に好適に用いることができる電池ケース及び電池ケース用表面処理鋼板に関する。
背景技術
従来、アルカリマンガン電池やニッケル−カドミウム電池などの強アルカリ液を封入する電池ケースには、冷延鋼帯を電池ケースにプレス成形後、バレルめっきする方法またはニッケルめっき鋼帯を電池ケースにプレス成形する方法が採用されてきた。このように、アルカリマンガン電池やニッケル−カドミウム電池などの電池用途に、ニッケルめっきが使用される理由は、これら電池は主として強アルカリ性の水酸化カリウムを電解液としているため、耐アルカリ腐食性にニッケルが強いこと、さらに電池を外部端子に接続する場合、安定した接触抵抗をニッケルは有していること、更には電池製造時、各構成部品を溶接し、電池に組み立てられる際、スポット溶接が行われるが、ニッケルはスポット溶接性にも優れるという利点があるからである。
ところで、近年、バレルめっき法は、めっき厚み、特にケース内面側にはニッケルめっきの均一に付着させることが困難で、めっき厚みのバラツキが大きく、品質の不安定性から、鋼帯に予めニッケルめっきが施されたプレめっき法が主流を占めてきた。なお、プレめっき法についても主として耐食性を向上させるため、ニッケルめっき後、熱拡散処理を施こす方法が適用されるようになってきた。
近年、電池ケースのプレス成形法として、電池容量の増大を図るため、深絞り成形法に替わって、薄肉化する方法としてＤＩ（ｄｒａｗｉｎｇ ａｎｄ ｉｒｏｎｉｎｇ）成形法も用いられるようになった（特公平７−９９６８６号公報参照）。このＤＩ成形法やＤＴＲ（ｄｒａｗｉｎｇ ｔｈｉｎ ａｎｄ ｒｅｄｒａｗ）成形法は、底面厚みよりケース側壁厚みが薄くなる分だけ、正極、負極活物質が多く充填でき、電池の容量増加が図れるとともに、ケース底が厚いため、電池の耐圧強度の向上をも得られる利点がある。
更に、近年、アルカリマンガン電池あるいはニッケル−水素電池の需要が増加しており、それに伴って電池作製の自動化が進んでいる。このため、プレス成形した電池ケースは、自動でベルトコンベアで電池ケース洗浄装置あるいは電池作製装置へ搬送する。しかし、電池外面側のすべり性が悪いと、電池ケースがベルトコンベアの途中で止まり、電池洗浄装置あるいは電池作製工程への電池ケースの供給が遅れ、作業効率が悪くなる。
近年、深絞り成形法、ＤＩ成形法あるいはＤＴＲ成形法で作製した電池ケースは、電池を作るために多量の缶をベルトコンベアに乗せて流す。しかし、従来の缶外面の最表層が光沢ニッケルめっきでは、スムーズに流れにくく、電池ケースの供給がスポット的になりがちであった。特に、ベルトコンベアで流した電池ケースを一列づつ並べる工程に入る時、缶外面の最表層が光沢ニッケルでは詰まりやすい。
本発明は、光沢性に優れ、流れ性にも優れた電池ケース及び該電池ケースを作製するために好適に用いることができる表面処理鋼板を提供することを技術的課題とする。
発明の開示
そこで、本発明者は、このような観点から、深絞り成形法、ＤＩ成形法ならびにＤＴＲ成形法で作製した電池ケースにおいて、缶外面の最表層に光沢ニッケル−コバルト合金めっき層を有すると、ベルトコンベアでの電池ケースの流れ性が優れていることを見いだしたものである。電池ケースの流れ性は、ケース外面側が硬くて、摩擦係数が小さいと良好であると推定される。また、コバルトを添加することにより、めっき表面の光沢度は向上することを見いだした。
前記目的を達成するため、本発明の電池ケースは、鋼板からなるめっき原板の缶内面に無光沢ニッケルめっきを施し、缶外面に下層として無光沢ニッケルめっきと、上層として光沢ニッケル−コバルト合金めっきの２層めっきを施した表面処理鋼鈑を深絞り成形法、ＤＩ成形法又はＤＴＲ成形法によって成形して得られるものであることを特徴とする。
本発明の電池ケースは、鋼板からなるめっき原板の缶内面に半光沢ニッケルめっきを施し、缶外面に下層として半光沢ニッケルめっきと、上層として光沢ニッケル−コバルト合金めっきの２層めっきを施した表面処理鋼鈑を深絞り成形法、ＤＩ成形法又はＤＴＲ成形法によって成形して得られるものであることを特徴とする。
本発明の電池ケースは、前記光沢ニッケル−コバルト合金めっきのコバルト含有量を０．５〜１０重量％として得られるものであることを特徴とする。
本発明の電池ケースは、前記光沢ニッケル−コバルト合金めっきの厚みを、０．５〜４μｍして得られるものであることを特徴とする。
本発明の表面処理鋼板は、鋼板からなるめっき原板の缶内面に無光沢ニッケルめっきを施し、缶外面に下層として無光沢ニッケルめっきと、上層として光沢ニッケル−コバルト合金めっきの２層めっきを施していることを特徴とする。
本発明の表面処理鋼板は、鋼板からなるめっき原板の缶内面に半光沢ニッケルめっきを施し、缶外面に下層として半光沢ニッケルめっきと、上層として光沢ニッケル−コバルト合金めっきの２層めっきを施していることを特徴とする。
本発明の表面処理鋼板は、前記光沢ニッケル−コバルト合金めっきのコバルト含有量を０．５〜１０重量％とすることを特徴とする。
本発明の表面処理鋼板は、前記光沢ニッケル−コバルト合金めっきの厚みを、０．５〜４μｍとすることを特徴とする。
発明を実施するための最良の形態
上記した電池ケース及び表面処理鋼板における光沢ニッケル−コバルト合金めっきの生成について述べると、ワット浴、スルファミン酸浴に硫酸コバルトを添加した場合、コバルトがニッケルと共析し、その結果、共析めっき層はめっき皮膜中のコバルト含有量の増加と共に、光沢度が増し、また、めっき皮膜層の硬さが高くなる。具体的には、光沢ニッケルめっきの硫酸浴のめっき光沢度は、コバルト無添加の場合、４６０〜４７０（ＪＩＳ Ｚ ８７４１、鏡面光沢度−測定方法）であるのに対し、一例としてコバルト含有量が１．０％では、５０７〜５２５（ＪＩＳ Ｚ ８７４１、鏡面光沢度−測定方法）と高くなる。
なお、本発明は、電池ケースの成形法によらないで、例えば、深絞り成形法、ＤＩ成形法やＤＴＲ成形法によらないで、缶の流れ性の改善が得られ、好適に用いることができる。
ところで、光沢ニッケル−コバルト合金めっきのコバルト含有量は０．５％〜１０％の範囲が好適である。コバルト含有量が０．５％未満では、コバルト添加による光沢度アップあるいは缶の流れ性への効果がなく、一方、コバルト含有量が１０％より大きい場合では、缶の流れ性の効果が飽和に達し、かつコバルトが高価な貴金属であることから不経済であるからである。
表面処理鋼板のめっき厚みは、本発明の光沢ニッケル−コバルト合金めっきでは、ケース外面相当側は１．０〜４．０μｍの範囲が望ましい。
ケース外面側のめっき厚みが１．０μｍ未満では、光沢度の向上あるいは電池ケースの流れ性に効果がない。また、耐食性が十分ではなく、電池ケースのプレス工程、電池作製工程ならびに長期保存中での錆発生により、１．０μｍ以上が必要だからである。めっき厚みが４．０μｍを超えると、電池ケースの流れ性改善の効果が飽和に達しており、それ以上厚くすることは不経済であるからである。
表面処理鋼板の母材となる鋼板、即ち、めっき原板としては、通常、低炭素アルミキルド鋼が好適に用いられる。さらに、ニオブ、チタンを添加し、非時効性極低炭素鋼（炭素０．０１％未満）から製造された冷延鋼帯も用いられる。
そして、通常法により、冷延後、電解清浄、焼鈍、調質圧延した鋼帯をめっき原板とする。その後、このめっき原板を用い、無光沢ニッケルめっき、半光沢ニッケルめっきあるいは、光沢ニッケル−コバルト合金めっきを行い、表面処理鋼板を作製する。
めっき浴は公知の硫酸浴、スルファミン酸浴のいずれでもかまわないが、浴管理が比較的容易な硫酸浴が好適である。両めっき浴とも、めっき皮膜中のコバルトとニッケルとの析出割合は、めっき浴中での濃度比よりも数倍高いので、アノードはニッケルアノードとし、コバルトイオンの供給はスルファミン酸塩または硫酸塩の形で添加することが可能である。
実施例
本発明について、さらに、以下の実施例を参照して具体的に説明する。
板厚０．２５ｍｍならびに０．４ｍｍの冷間圧延、焼鈍、調質圧延済の低炭素アルミキルド鋼板を、それぞれ、めっき原板とした。両めっき原板の鋼化学組成は、共に、下記の通りである。
Ｃ：０．０４％（％は重量％，以下同じ）
Ｍｎ：０．２２％
Ｓｉ：０．０１％
Ｐ：０．０１２％
Ｓ：０．００６％
Ａｌ：０．０．４８％
Ｎ：０．００２５％
上記めっき原板を、常法により、アルカリ電解脱脂、水洗、硫酸浸漬、水洗後の前処理を行った後、通常の無光沢ニッケルめっきまたは半光沢ニッケルめっきを両面に行った。次に下記の条件で缶外面側になる光沢ニッケル−コバルト合金めっきを行ない、表面処理鋼板を作製した。
１）無光沢ニッケルめっき
下記の硫酸ニッケル浴を用いて無光沢ニッケルめっきを行った。
浴組成
硫酸ニッケル NiSO4・6H2O 300g/L
塩化ニッケル NiCl2・6H2O 45g/L
硼酸 H3BO3 30g/L
浴pH：4（硫酸で調整）
撹拌：空気撹拌
浴温度：60℃
アノード：Ｓペレット（ＩＮＣＯ社製商品名、球状）をチタンバスケットに装填してポリプロレン製バッグで覆ったものを使用。
２）半光沢ニッケルめっき
硫酸ニッケル浴に半光沢剤として不飽和アルコールのポリオキシ−エチレン付加物および不飽和カルボン酸ホルムアルデヒドを適宜添加して半光沢ニッケルめっきを行った。
浴組成
硫酸ニッケル NiSO4・6H2O 300g/L
塩化ニッケル NiCl2・6H2O 45g/L
硼酸 H3BO3 30g/L
不飽和アルコールのポリオキシ−エチレン付加物 3.0g/L
不飽和カルボン酸ホルムアルデヒド 3.0g/L
浴pH：4（硫酸で調整）
撹拌：空気撹拌
浴温度：60℃
アノード：Ｓペレット（ＩＮＣＯ社製商品名、球状）をチタンバスケットに装填してポリプロレン製バッグで覆ったものを使用。
３）光沢ニッケル−コバルト合金めっき
硫酸ニッケル浴に硫酸コバルトを適宜添加してニッケルめっき層中にコバルトを含有させた。
浴組成
硫酸ニッケル NiSO4・6H2O 300g/L
塩化ニッケル NiCl2・6H2O 45g/L
硫酸コバルト CoSO4・6H2O （適宜）
硼酸 H3BO3 30g/L
含窒素複素環化合物 0.6g/L
含窒素脂肪族化合物 2.0g/L
浴pH：4（硫酸で調整）
撹拌：空気撹拌
浴温度：60℃
アノード：Ｓペレット（ＩＮＣＯ社製商品名、球状）をチタンバスケットに装填してポリプロレン製バッグで覆ったものを使用。
上記の条件で、硫酸コバルト添加量および電解時間を変えて、めっき皮膜中のコバルト含有量、めっき厚みを変化させた。
（電池ケース作製）
ＤＩ成形法による電池ケースの作製は、板厚０．４ｍｍの上記めっき鋼板を用い直径４１ｍｍのブランク径から直径２０．５ｍｍのカッピングの後、ＤＩ成形機でリドロ−および２段階のしごき成形を行って外径１３．８ｍｍ、ケース壁０．２０ｍｍ、高さ５６ｍｍに成形した。最終的に上部をトリミングして、高さ４９．３ｍｍのＬＲ６型電池ケースを作製した。
また、ＤＴＲ成形法による電池ケースの作製は、板厚０．２５ｍｍのめっき鋼板を用い、ブランク径５８ｍｍに打ち抜き、数回の絞り、再絞り成形によって外径１３．８ｍｍ、ケース壁０．２０ｍｍ、高さ４９．３ｍｍのＬＲ６型電池ケースを作製した。
更に、深絞り成形法による電池ケースの作製は、板厚０．２５ｍｍのめっき鋼板を用い、ブランク径５７ｍｍに打ち抜き、数回の絞り、再絞り成形によって外径１３．８ｍｍ、ケース壁０．２５ｍｍ、高さ４９．３ｍｍのＬＲ６型電池ケースを作製した。
（光沢度測定）
光沢度は光沢ニッケル−コバルト合金めっき後の表面処理鋼板を用いて、光沢ニッケル−コバルト合金めっき面をＪＩＳ Ｚ ８７４１に準じて測定した。その結果を表１に示す。
（電池ケースの流れ性）
電池ケース１００個をベルトコンベアに乗せ、ベルトコンベアで運んだ先では、電池ケース１個のみ通すように幅を狭くして電池ケースの流れ性を見た。比較例１より電池ケース１００個がベルトコンベアを通る時間が短い場合を○と評価した。その結果を表１に示す。
最表層に光沢ニッケル−コバルト合金めっきを有する表面処理鋼板は、光沢度が光沢ニッケルめっきに比べて高い。また、深絞り成形法、ＤＩ成形法またはＤＴＲ成形法によって成形して得た外面側の最表層に光沢ニッケル−コバルト合金めっきを有する電池ケースは、外面側に光沢ニッケルめっきを有する電池ケースに比べて、電池ケースの流れ性が良好で、電池作製作業がスムーズに行える。TECHNICAL FIELD The present invention relates to a container enclosing an alkaline solution, more specifically a battery outer case such as an alkaline manganese battery or a nickel-cadmium battery, and a battery case and a surface for the battery case that can be suitably used for producing the case. It relates to a treated steel plate.
BACKGROUND ART Conventionally, for battery cases that enclose a strong alkaline solution such as an alkaline manganese battery or a nickel-cadmium battery, a cold-rolled steel strip is press-molded into the battery case and then barrel-plated or a nickel-plated steel strip is used as the battery case. A press molding method has been adopted. As described above, nickel plating is used for battery applications such as alkaline manganese batteries and nickel-cadmium batteries. These batteries are mainly made of strong alkaline potassium hydroxide as an electrolyte, so that nickel corrosion resistance is improved. In addition, when connecting batteries to external terminals, nickel has stable contact resistance.Moreover, when manufacturing batteries, each component is welded, and spot welding is performed when assembled into batteries. However, nickel is advantageous in that it has excellent spot weldability.
By the way, in recent years, with the barrel plating method, it is difficult to uniformly deposit nickel plating on the plating thickness, particularly on the inner surface of the case. The applied pre-plating method has been dominant. As for the pre-plating method, in order to mainly improve the corrosion resistance, a method of applying a thermal diffusion treatment after nickel plating has been applied.
In recent years, in order to increase battery capacity as a press forming method for battery cases, a DI (drawing and ironing) forming method has been used as a thinning method instead of the deep drawing forming method (Japanese Patent Publication No. 7). -99686). This DI molding method and DTR (drawing thin and redraw) molding method can fill more positive and negative electrode active materials as the case side wall thickness is thinner than the bottom surface thickness, increasing the battery capacity and thickening the case bottom. Therefore, there is an advantage that an improvement in the pressure strength of the battery can be obtained.
Furthermore, in recent years, the demand for alkaline manganese batteries or nickel-hydrogen batteries has increased, and accordingly, the production of batteries has been automated. For this reason, the press-molded battery case is automatically conveyed to a battery case cleaning device or a battery manufacturing device by a belt conveyor. However, if the sliding property on the battery outer surface side is poor, the battery case stops in the middle of the belt conveyor, the supply of the battery case to the battery cleaning device or the battery manufacturing process is delayed, and the work efficiency is deteriorated.
In recent years, battery cases manufactured by the deep drawing method, DI molding method, or DTR molding method flow a large number of cans on a belt conveyor to make a battery. However, when the outermost surface of the conventional can outer surface is bright nickel plating, it is difficult to flow smoothly and the battery case supply tends to be spotted. In particular, when entering the process of arranging the battery cases flown on the belt conveyor one by one, the outermost layer on the outer surface of the can is easily clogged with bright nickel.
This invention makes it a technical subject to provide the battery case which was excellent in glossiness, and was excellent also in the fluidity | liquidity, and the surface treatment steel plate which can be used suitably in order to produce this battery case.
DISCLOSURE OF THE INVENTION Accordingly, from such a viewpoint, the present inventor has a bright nickel-cobalt alloy plating layer on the outermost layer of the outer surface of the can in battery cases produced by the deep drawing method, DI molding method and DTR molding method. Then, it has been found that the flowability of the battery case on the belt conveyor is excellent. The flowability of the battery case is estimated to be good when the case outer surface is hard and the friction coefficient is small. Further, it has been found that the glossiness of the plating surface is improved by adding cobalt.
In order to achieve the above object, the battery case of the present invention is formed by applying a matte nickel plating to the inner surface of a plating base plate made of a steel plate, a matte nickel plating as a lower layer on the outer surface of the can, and a bright nickel-cobalt alloy plating as an upper layer. It is characterized in that it is obtained by forming a surface-treated steel plate subjected to two-layer plating by a deep drawing method, a DI forming method or a DTR forming method.
The battery case of the present invention has a semi-glossy nickel plating on the inner surface of a plating plate made of a steel plate, and a surface on which the outer surface of the can is subjected to two-layer plating of a semi-glossy nickel plating as a lower layer and a bright nickel-cobalt alloy plating as an upper layer It is characterized by being obtained by forming a treated steel sheet by a deep drawing method, a DI forming method or a DTR forming method.
The battery case of the present invention is obtained by setting the cobalt content of the bright nickel-cobalt alloy plating to 0.5 to 10% by weight.
The battery case of the present invention is obtained by setting the thickness of the bright nickel-cobalt alloy plating to 0.5 to 4 μm.
The surface-treated steel sheet of the present invention is obtained by applying a matte nickel plating on the inner surface of a plating base plate made of a steel plate, and applying a two-layer plating of a matte nickel plating as a lower layer and a bright nickel-cobalt alloy plating as an upper layer on the outer surface of the can It is characterized by being.
The surface-treated steel sheet of the present invention is obtained by performing semi-bright nickel plating on the inner surface of a plating original plate made of a steel plate, and performing two-layer plating of semi-bright nickel plating as a lower layer and bright nickel-cobalt alloy plating as an upper layer on the outer surface of the can. It is characterized by being.
The surface-treated steel sheet of the present invention is characterized in that the cobalt content of the bright nickel-cobalt alloy plating is 0.5 to 10% by weight.
The surface-treated steel sheet of the present invention is characterized in that the thickness of the bright nickel-cobalt alloy plating is 0.5 to 4 μm.
BEST MODE FOR CARRYING OUT THE INVENTION The production of bright nickel-cobalt alloy plating in the above battery case and surface-treated steel sheet will be described. When cobalt sulfate is added to a watt bath or a sulfamic acid bath, cobalt is co-deposited with nickel. As a result, the eutectoid plated layer increases in gloss as the cobalt content in the plated film increases, and the hardness of the plated film layer increases. Specifically, the plating gloss of the bright nickel plating sulfuric acid bath is 460 to 470 (JIS Z 8741, specular gloss-measuring method) when no cobalt is added, but the cobalt content is an example. At 1.0%, it becomes as high as 507 to 525 (JIS Z 8741, specular gloss-measurement method).
Note that the present invention can be used suitably because it can improve the flowability of the can without depending on the battery case molding method, for example, the deep drawing method, the DI molding method or the DTR molding method. it can.
By the way, the cobalt content of the bright nickel-cobalt alloy plating is preferably in the range of 0.5% to 10%. When the cobalt content is less than 0.5%, there is no effect on the glossiness or can flowability due to the addition of cobalt, whereas when the cobalt content is greater than 10%, the flow effect of the can is saturated. This is because it is expensive and cobalt is an expensive noble metal.
In the bright nickel-cobalt alloy plating of the present invention, the plating thickness of the surface-treated steel sheet is preferably in the range of 1.0 to 4.0 μm on the case outer surface equivalent side.
When the plating thickness on the case outer surface side is less than 1.0 μm, there is no effect on the improvement of the glossiness or the flowability of the battery case. Moreover, corrosion resistance is not sufficient, and 1.0 μm or more is necessary due to rust generation during the battery case pressing process, battery manufacturing process, and long-term storage. This is because if the plating thickness exceeds 4.0 μm, the effect of improving the flowability of the battery case reaches saturation, and it is uneconomical to increase the thickness further.
As a steel plate that serves as a base material for the surface-treated steel plate, that is, a plating original plate, usually, a low carbon aluminum killed steel is suitably used. Furthermore, a cold-rolled steel strip produced by adding niobium and titanium and made from non-aging ultra-low carbon steel (carbon less than 0.01%) is also used.
And the steel strip which carried out the electrolytic cleaning, the annealing, and the temper rolling after the cold rolling by a normal method is used as a plating original plate. Then, using this plating base plate, matte nickel plating, semi-bright nickel plating or bright nickel-cobalt alloy plating is performed to produce a surface-treated steel sheet.
The plating bath may be either a known sulfuric acid bath or a sulfamic acid bath, but a sulfuric acid bath whose bath management is relatively easy is suitable. In both plating baths, the deposition ratio of cobalt and nickel in the plating film is several times higher than the concentration ratio in the plating bath, so the anode is a nickel anode, and the supply of cobalt ions is sulfamate or sulfate. It can be added in the form.
Examples The present invention will be further described with reference to the following examples.
Cold rolled, annealed and temper-rolled low carbon aluminum killed steel sheets having a thickness of 0.25 mm and 0.4 mm were used as plating original sheets, respectively. The steel chemical composition of both plating original plates is as follows.
C: 0.04% (% is% by weight, the same applies hereinafter)
Mn: 0.22%
Si: 0.01%
P: 0.012%
S: 0.006%
Al: 0.0.48%
N: 0.0025%
The plating original plate was subjected to alkaline electrolytic degreasing, water washing, sulfuric acid immersion, and pretreatment after water washing by a conventional method, and then normal matte nickel plating or semi-bright nickel plating was performed on both sides. Next, bright nickel-cobalt alloy plating on the outer surface side of the can was performed under the following conditions to produce a surface-treated steel sheet.
1) Matte nickel plating Matte nickel plating was performed using the following nickel sulfate bath.
Bath composition Nickel sulfate NiSO 4・ 6H 2 O 300g / L
Nickel chloride NiCl 2・ 6H 2 O 45g / L
Boric acid H 3 BO 3 30g / L
Bath pH: 4 (adjusted with sulfuric acid)
Stirring: Air stirring bath temperature: 60 ° C
Anode: S pellets (trade name, manufactured by INCO, spherical shape) loaded in a titanium basket and covered with a polyprolene bag are used.
2) Semi-bright nickel plating Semi-bright nickel plating was performed by appropriately adding polyoxy-ethylene adduct of unsaturated alcohol and unsaturated carboxylic acid formaldehyde as a semi-bright agent to a nickel sulfate bath.
Bath composition Nickel sulfate NiSO 4・ 6H 2 O 300g / L
Nickel chloride NiCl 2・ 6H 2 O 45g / L
Boric acid H 3 BO 3 30g / L
Polyoxy-ethylene adduct of unsaturated alcohol 3.0g / L
Unsaturated carboxylic acid formaldehyde 3.0g / L
Bath pH: 4 (adjusted with sulfuric acid)
Stirring: Air stirring bath temperature: 60 ° C
Anode: S pellets (trade name, manufactured by INCO, spherical shape) loaded in a titanium basket and covered with a polyprolene bag are used.
3) Bright nickel-cobalt alloy plating Cobalt sulfate was appropriately added to a nickel sulfate bath to contain cobalt in the nickel plating layer.
Bath composition Nickel sulfate NiSO 4・ 6H 2 O 300g / L
Nickel chloride NiCl 2・ 6H 2 O 45g / L
Cobalt sulfate CoSO 4 · 6H 2 O (as appropriate)
Boric acid H 3 BO 3 30g / L
Nitrogen-containing heterocyclic compound 0.6g / L
Nitrogen-containing aliphatic compound 2.0g / L
Bath pH: 4 (adjusted with sulfuric acid)
Stirring: Air stirring bath temperature: 60 ° C
Anode: S pellets (trade name, manufactured by INCO, spherical shape) loaded in a titanium basket and covered with a polyprolene bag are used.
Under the above conditions, the cobalt sulfate content and the plating thickness in the plating film were changed by changing the addition amount of cobalt sulfate and the electrolysis time.
(Battery case fabrication)
The battery case is manufactured by the DI molding method using the above-mentioned plated steel sheet having a thickness of 0.4 mm, cupping from a blank diameter of 41 mm to a diameter of 20.5 mm, and then performing redo and two-stage ironing with a DI molding machine. The outer diameter was 13.8 mm, the case wall was 0.20 mm, and the height was 56 mm. Finally, the upper part was trimmed to produce an LR6 type battery case having a height of 49.3 mm.
In addition, the battery case by the DTR molding method is manufactured by using a plated steel plate having a thickness of 0.25 mm, punching out to a blank diameter of 58 mm, drawing several times, and redrawing to form an outer diameter of 13.8 mm, a case wall of 0.20 mm An LR6 type battery case having a height of 49.3 mm was produced.
Further, the battery case was manufactured by deep drawing using a plated steel plate having a thickness of 0.25 mm, punched to a blank diameter of 57 mm, drawn several times, and redrawed to give an outer diameter of 13.8 mm and a case wall of 0.25 mm. An LR6 type battery case having a height of 49.3 mm was produced.
(Glossiness measurement)
The glossiness was measured in accordance with JIS Z 8741 using a surface-treated steel sheet after plating with a bright nickel-cobalt alloy, and the bright nickel-cobalt alloy plated surface. The results are shown in Table 1.
(Battery case flowability)
When 100 battery cases were put on a belt conveyor and carried by the belt conveyor, the width was narrowed so that only one battery case was passed, and the flowability of the battery case was observed. The case where 100 battery cases passed the belt conveyor for a short time compared with the comparative example 1 was evaluated as (circle). The results are shown in Table 1.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11550399 | 1999-04-22 | ||
| PCT/JP2000/002601 WO2000065671A1 (en) | 1999-04-22 | 2000-04-20 | Battery case and surface treated steel sheet for battery case |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP3631143B2 true JP3631143B2 (en) | 2005-03-23 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000614519A Expired - Lifetime JP3631143B2 (en) | 1999-04-22 | 2000-04-20 | Battery case and surface-treated steel sheet for battery case |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3631143B2 (en) |
| AU (1) | AU3841000A (en) |
| WO (1) | WO2000065671A1 (en) |
Cited By (1)
| 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 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4808834B2 (en) | 2000-08-04 | 2011-11-02 | 東洋鋼鈑株式会社 | Surface-treated steel sheet for battery case |
| CN1312787C (en) * | 2002-04-22 | 2007-04-25 | 东洋钢钣株式会社 | Surface treated steel sheet for battery case, battery case and battery using the case |
| JP5593167B2 (en) | 2010-08-26 | 2014-09-17 | Ｆｄｋエナジー株式会社 | Alkaline battery |
| TWI451005B (en) | 2011-04-07 | 2014-09-01 | Nippon Steel & Sumitomo Metal Corp | Ni containing surface treated steel sheet for can and producing method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW338071B (en) * | 1996-05-09 | 1998-08-11 | Toyo Koban Kk | A battery container and surface treated steel sheet for battery container |
| TW457305B (en) * | 1996-05-23 | 2001-10-01 | Toyo Kohan Co Ltd | Plated steel sheet for battery container, manufacturing method therefor, and battery container and battery using the same |
| CN1212680C (en) * | 1996-09-03 | 2005-07-27 | 东洋钢钣株式会社 | Surface treatment steel plate for battery case, battery case and battery using the case |
| JPH10172521A (en) * | 1996-12-12 | 1998-06-26 | Toshiba Battery Co Ltd | Alkaline battery |
-
2000
- 2000-04-20 JP JP2000614519A patent/JP3631143B2/en not_active Expired - Lifetime
- 2000-04-20 AU AU38410/00A patent/AU3841000A/en not_active Abandoned
- 2000-04-20 WO PCT/JP2000/002601 patent/WO2000065671A1/en active Application Filing
Cited By (1)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU3841000A (en) | 2000-11-10 |
| WO2000065671A1 (en) | 2000-11-02 |
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