JP2001279490A - ONE SIDE Ni PLATED STEEL SHEET HAVING HIGH LUSTER AND REDUCED CONTACT RESISTANCE FOR NEGATIVE AND POSITIVE POLE CANS OF LITHIUM BUTTON CELL - Google Patents
ONE SIDE Ni PLATED STEEL SHEET HAVING HIGH LUSTER AND REDUCED CONTACT RESISTANCE FOR NEGATIVE AND POSITIVE POLE CANS OF LITHIUM BUTTON CELLInfo
- Publication number
- JP2001279490A JP2001279490A JP2000094166A JP2000094166A JP2001279490A JP 2001279490 A JP2001279490 A JP 2001279490A JP 2000094166 A JP2000094166 A JP 2000094166A JP 2000094166 A JP2000094166 A JP 2000094166A JP 2001279490 A JP2001279490 A JP 2001279490A
- Authority
- JP
- Japan
- Prior art keywords
- plating layer
- stainless steel
- contact resistance
- plating
- bright
- 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.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、接触抵抗が低く、しか
も高光沢のリチウムボタン電池の正極缶及び負極缶用片
面Ｎｉめっき鋼板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a single-sided Ni-plated steel sheet for a positive electrode can and a negative electrode can of a lithium button battery having low contact resistance and high gloss.
【０００２】[0002]
【従来の技術】リチウム乾電池は、他の一次電池に比較
して放電電圧が３Ｖと高く、放電中の電圧が安定してお
り、しかも放電寿命が極めて長い。このような長所を活
用し、ボタン電池として多用されている。リチウムボタ
ン電池は、正極缶１と負極缶２で構成される電池缶容器
に、二酸化マンガン，フッ化水素等の正極活性物質３及
び負極活性物質４（リチウム塩）がセパレータ５を介し
て充填され、正極缶１と負極缶２との間を絶縁性パッキ
ング６で絶縁している（図１）。炭酸プロピレン等の有
機溶媒を含浸させたセパレータ５を介して酸化還元反応
が生起され、反応エネルギーが電気エネルギーとして取
り出される。2. Description of the Related Art A lithium dry battery has a discharge voltage as high as 3 V as compared with other primary batteries, has a stable voltage during discharge, and has a very long discharge life. Utilizing such advantages, it is widely used as a button battery. In a lithium button battery, a battery can container composed of a positive electrode can 1 and a negative electrode can 2 is filled with a positive electrode active material 3 such as manganese dioxide and hydrogen fluoride and a negative electrode active material 4 (lithium salt) via a separator 5. The insulation between the positive electrode can 1 and the negative electrode can 2 is provided by an insulating packing 6 (FIG. 1). An oxidation-reduction reaction occurs through the separator 5 impregnated with an organic solvent such as propylene carbonate, and the reaction energy is extracted as electric energy.
【０００３】正極缶１及び負極缶２の材料としては、非
水溶液に接する雰囲気で優れた耐食性が要求されること
からステンレス鋼を基材に使用し、ケース外面の接触抵
抗を下げるためのＮｉめっきを施している。負極活性物
質４のリチウム塩が外気の水分と反応すると発熱が発生
することから、電池缶を完全密閉することが重要であ
る。負極缶２は絶縁性パッキング６と接するカシメ部を
厳しい曲げ加工を施して密閉するため、曲げ加工部に皺
や割れが生じない材料として加工性に優れたＳＵＳ３０
４に代表されるオーステナイト系ステンレス鋼が使用さ
れる。正極缶１は、負極缶２に比較して軽度の加工です
むため、材料コストを考慮してＳＵＳ４３０等のフェラ
イト系ステンレス鋼が使用されている。As a material for the positive electrode can 1 and the negative electrode can 2, stainless steel is used as a base material because excellent corrosion resistance is required in an atmosphere in contact with a non-aqueous solution, and Ni plating is applied to reduce the contact resistance on the outer surface of the case. Has been given. When the lithium salt of the negative electrode active material 4 reacts with the moisture of the outside air, heat is generated. Therefore, it is important to completely seal the battery can. Since the negative electrode can 2 is tightly bent and tightly sealed at the crimped portion in contact with the insulating packing 6, SUS30 which is excellent in workability as a material which does not cause wrinkles or cracks in the bent portion.
Austenitic stainless steel represented by No. 4 is used. Since the positive electrode can 1 requires less processing than the negative electrode can 2, ferritic stainless steel such as SUS430 is used in consideration of material costs.
【０００４】[0004]
【発明が解決しようとする課題】正極缶１及び負極缶２
の外面に施されるＮｉめっきは、接触抵抗を下げると共
に、ボタン電池に光沢を付与して見栄えを改善してい
る。光沢のあるＮｉめっき層の形成には、ベンゼン，ト
ルエン，ナフタレンスルホン酸ナトリウム，サッカリン
等の光沢剤を含むめっき浴が使用されるが、Ｎｉめっき
層に取り込まれた光沢剤は大気雰囲気中で酸化されやす
い。そのため、光沢Ｎｉめっきを施した電池缶では、光
沢剤の酸化分解に起因して接触抵抗が高くなり、電池寿
命が短くなる。SUMMARY OF THE INVENTION Positive electrode can 1 and negative electrode can 2
The Ni plating applied to the outer surface of (1) lowers the contact resistance and imparts gloss to the button battery to improve the appearance. To form a bright Ni plating layer, a plating bath containing a brightener such as benzene, toluene, sodium naphthalenesulfonate, and saccharin is used, but the brightener incorporated in the Ni plating layer is oxidized in the atmosphere. Easy to be. Therefore, in a battery can that has been subjected to bright Ni plating, the contact resistance increases due to the oxidative decomposition of the brightener, and the battery life is shortened.
【０００５】[0005]
【課題を解決するための手段】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、光沢Ｎｉめっき
層の上に薄い無光沢Ｎｉめっき層を形成することによ
り、光沢を損なうことなく低い接触抵抗が維持されるリ
チウムボタン電池を提供することを目的とする。本発明
に従ったリチウムボタン電池缶は、加工性の良好なオー
ステナイト系ステンレス鋼を負極缶の基材とし、正極缶
の基材には比較的安価なフェライト系ステンレス鋼を使
用している。何れのステンレス鋼も表面粗さがＲａ０．
０５μｍ以下に調整され、光沢Ｎｉめっき層を介して層
厚０．０１〜０．３μｍの無光沢Ｎｉめっき層が形成さ
れている。SUMMARY OF THE INVENTION The present invention has been devised in order to solve such a problem, and the gloss is reduced by forming a thin matte Ni plating layer on a bright Ni plating layer. An object of the present invention is to provide a lithium button battery in which a low contact resistance is maintained without loss. The lithium button battery can according to the present invention uses austenitic stainless steel having good workability as a base material of a negative electrode can, and uses a relatively inexpensive ferritic stainless steel as a base material of a positive electrode can. Each stainless steel has a surface roughness of Ra0.
A matte Ni plating layer having a thickness of 0.01 to 0.3 μm is formed with a thickness of 0.01 μm or less and a bright Ni plating layer interposed therebetween.
【０００６】[0006]
【実施の形態】負極缶の基材には、過酷な曲げ加工を受
けることから加工性の良好なオーステナイト系ステンレ
ス鋼が使用される。加工性の低い基材を使用すると、絶
縁性パッキング６に接するカシメ部を曲げ加工で成形す
る際に液漏れの原因となるクラックが発生し易くなる。
他方、正極缶の基材は、負極缶に比較して加工度が低い
ことから安価なフェライト系ステンレス鋼が使用され
る。負極缶用オーステナイト系ステンレス鋼及び正極缶
用フェライト系ステンレス鋼は、何れも良好な光沢を確
保する上から表面粗さがＲａ０．０５μｍ以下に調整さ
れる。表面粗さをＲａ０．０５μｍ以下にすると、その
上に形成されるＮｉめっき層の表面に基材表面の凹凸が
反映されず、数μｍ程度の薄い光沢Ｎｉめっき層であっ
ても十分な光沢が発現する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Austenitic stainless steel having good workability is used as a base material of a negative electrode can because it is subjected to severe bending. When a base material having low workability is used, cracks that cause liquid leakage easily occur when a crimped portion in contact with the insulating packing 6 is formed by bending.
On the other hand, as the base material of the positive electrode can, inexpensive ferritic stainless steel is used because it has a lower workability than the negative electrode can. The surface roughness of each of the austenitic stainless steel for the negative electrode can and the ferritic stainless steel for the positive electrode can is adjusted to Ra 0.05 μm or less in order to ensure good gloss. When the surface roughness is set to Ra 0.05 μm or less, the surface of the Ni plating layer formed thereon does not reflect the unevenness of the substrate surface, and sufficient gloss is obtained even with a thin gloss Ni plating layer of about several μm. Express.
【０００７】負極缶用オーステナイト系ステンレス鋼及
び正極缶用フェライト系ステンレス鋼としては、結晶粒
度番号６．５〜９．０の結晶粒度番号をもち、全伸びが
５０％以上の材料を使用することが好ましい。結晶粒度
番号が６．５未満になると、加工部の粒界にクラックが
発生し、肌荒れが生じやすくなる。他方、９．０を越え
る結晶粒度番号では、硬度が高すぎ、加工後の形状凍結
性が低下し、スプリングバックが大きく、電池缶の組立
てが困難になる。また、負極缶用オーステナイト系ステ
ンレス鋼及び正極缶用フェライト系ステンレス鋼は、５
０％以上の全伸び５０％をもつことが好ましい。全伸び
が５０％以上になると、過酷な加工が施されても皺，割
れ等が発生せず、アルカリ性電解液の漏出がない電池缶
が得られる。更に、電池缶形状への成形に材料の均一な
流れ込みを確保して形状精度の良好な負極缶及び正極缶
に成形する上から、０．２％耐力を４００Ｎ／ｍｍ2以
下にした材料の使用が好ましい。耐力が高すぎる材料で
は、成形時に材料の流れ込みが不均一になり、缶頭部に
肉余りのある形状不良が生じやすくなる。As the austenitic stainless steel for the negative electrode can and the ferritic stainless steel for the positive electrode can, use a material having a crystal grain size of 6.5 to 9.0 and a total elongation of 50% or more. Is preferred. If the crystal grain size number is less than 6.5, cracks occur at the grain boundaries of the processed portion, and the surface is likely to be rough. On the other hand, if the crystal grain size number exceeds 9.0, the hardness is too high, the shape freezing property after processing is reduced, the springback is large, and it becomes difficult to assemble the battery can. Austenitic stainless steel for negative electrode cans and ferritic stainless steel for positive electrode cans
Preferably, it has a total elongation of 0% or more and 50%. When the total elongation is 50% or more, wrinkles, cracks, and the like do not occur even under severe processing, and a battery can with no leakage of the alkaline electrolyte can be obtained. Furthermore, use of a material having a 0.2% proof stress of 400 N / mm 2 or less in order to form a negative electrode can and a positive electrode can with good shape accuracy by ensuring a uniform flow of the material into the battery can shape. Is preferred. In the case of a material having a too high proof stress, the inflow of the material during molding becomes non-uniform, and a defective shape with a large excess in the head of the can is likely to occur.
【０００８】負極缶及び正極缶の基材として使用される
ステンレス鋼の表面に、光沢を付与するために光沢Ｎｉ
めっき層が形成される。光沢Ｎｉめっきには、ベンゼ
ン，トルエン，ナフタレンスルホン酸ナトリウム，サッ
カリン等の光沢剤が添加された硫酸ニッケル，塩化ニッ
ケル，ホウ酸成分等を含む有機光沢めっき浴が使用され
る。めっき条件は使用するめっき浴組成によって異なる
が、たとえばｐＨ２．８〜５．５，浴温４０〜７０℃，
電流密度１〜１０Ａ／ｄｍ2の範囲で選定され、通電時
間を変化させることにより必要厚みの光沢Ｎｉめっき層
を形成する。めっきされるステンレス鋼は、電解脱脂、
酸洗後、めっき浴に浸漬され、必要厚みの光沢Ｎｉめっ
き層が形成される。このとき、基材として使用されるス
テンレス鋼の表面粗さがＲａ０．０５μｍ以下と極めて
平滑な表面に調整されているため、具体的には１μｍ以
上の比較的薄い光沢Ｎｉめっき層によっても十分な光沢
が付与される。また、基材に対する光沢ニッケルめっき
層の密着性を改善するため、予めＮｉストライクめっき
を施すことが好ましい。[0008] To impart gloss to the surface of stainless steel used as a base material for the negative electrode can and the positive electrode can, a glossy Ni is used.
A plating layer is formed. For bright Ni plating, an organic bright plating bath containing nickel sulfate, nickel chloride, boric acid components and the like to which a brightener such as benzene, toluene, sodium naphthalenesulfonate, and saccharin is added is used. The plating conditions vary depending on the composition of the plating bath used, for example, pH 2.8-5.5, bath temperature 40-70 ° C,
The current density is selected in the range of 1 to 10 A / dm 2 , and a bright Ni plating layer having a required thickness is formed by changing the energization time. Stainless steel to be plated is electrolytically degreased,
After pickling, the substrate is immersed in a plating bath to form a bright Ni plating layer having a required thickness. At this time, since the surface roughness of the stainless steel used as the base material is adjusted to an extremely smooth surface of Ra 0.05 μm or less, a relatively thin bright Ni plating layer of 1 μm or more is sufficient. Gloss is imparted. Further, in order to improve the adhesion of the bright nickel plating layer to the substrate, it is preferable to apply Ni strike plating in advance.
【０００９】光沢Ｎｉめっき層が形成された後、光沢度
を損なわない程度の膜厚、すなわち０．０１〜０．３μ
ｍの膜厚で無光沢Ｎｉめっき層を形成する。無光沢Ｎｉ
めっきには、たとえば光沢剤無添加の全塩化物浴や硫酸
ニッケル，塩化ニッケルホウ酸成分等を含むワット浴等
が使用される。めっき条件は使用するめっき浴組成によ
って異なるが、たとえばワット浴ではｐＨ１．５〜６．
０，浴温４０〜７０℃，電流密度２〜１０Ａ／ｄｍ2の
範囲で選定され、通電時間を変化させることにより必要
厚みの無光沢Ｎｉめっき層を形成する。無光沢Ｎｉめっ
き層は、光沢Ｎｉめっき層が外気に直接触れることを防
止する遮断膜として働き、光沢Ｎｉめっき層に含まれて
いる光沢剤の酸化を防止すると共に、表面の接触抵抗を
有効に低下させる。このような作用は、０．０１μｍ以
上の膜厚で顕著となる。しかし、無光沢Ｎｉめっき層が
厚すぎると光沢度が低下するので、膜厚の上限を０．３
μｍに設定することが好ましい。なお、本件明細書でい
う光沢Ｎｉめっき層は、光沢剤を添加しためっき浴を用
いた電気めっきで形成されためっき層を意味し、鏡のよ
うな高い反射率又は解像度を呈する。これに対し、光沢
剤を含まないめっき浴を用いた電気めっきで形成される
めっき層を無光沢Ｎｉめっき層という。After the bright Ni plating layer is formed, the thickness is such that the gloss is not impaired, that is, 0.01 to 0.3 μm.
A matte Ni plating layer is formed with a thickness of m. Matte Ni
For plating, for example, an all-chloride bath without a brightener or a Watt bath containing nickel sulfate, nickel chloride, boric acid and the like is used. The plating conditions vary depending on the composition of the plating bath used.
0, a bath temperature of 40 to 70 ° C., and a current density of 2 to 10 A / dm 2 , and a matte Ni plating layer having a required thickness is formed by changing the energizing time. The matte Ni plating layer acts as a blocking film that prevents the bright Ni plating layer from directly contacting the outside air, preventing oxidation of the brightener contained in the bright Ni plating layer and effectively reducing the surface contact resistance. Lower. Such an effect becomes remarkable at a film thickness of 0.01 μm or more. However, if the matte Ni plating layer is too thick, the glossiness is reduced.
It is preferable to set it to μm. In addition, the bright Ni plating layer referred to in the present specification means a plating layer formed by electroplating using a plating bath to which a brightener is added, and has a high mirror-like reflectance or resolution. On the other hand, a plating layer formed by electroplating using a plating bath containing no brightener is referred to as a matte Ni plating layer.
【００１０】[0010]
【実施例】表面粗さがＲａ０．０３６〜０．０７２μｍ
に調整された板厚０．２５ｍｍのＳＵＳ３０４オーステ
ナイト系ステンレス鋼板をめっき原板として使用し、電
解脱脂，酸洗の前処理を施した後、次のウッド浴に浸漬
し、膜厚０．２５μｍのＮｉストライクめっきを施し
た。 Example: Surface roughness Ra 0.036 to 0.072 μm
Using a SUS304 austenitic stainless steel plate having a thickness of 0.25 mm adjusted as described above as a plating base plate, performing a pretreatment of electrolytic degreasing and pickling, immersing it in the next wood bath, and forming a Ni5 layer having a thickness of 0.25 μm. Strike plating was applied.
【００１１】Ｎｉストライクメッキした後、０．５〜
８．２μｍの範囲で膜厚を変化させた光沢Ｎｉめっき層
を次の条件で形成した。 After Ni strike plating, 0.5 to
A bright Ni plating layer having a thickness changed in the range of 8.2 μm was formed under the following conditions.
【００１２】次いで、光沢Ｎｉめっき層の上に、０〜
０．７７μｍの範囲で膜厚を変化させた無光沢Ｎｉめっ
き層を次の条件で形成した。 Next, on the bright Ni plating layer,
A matte Ni plating layer whose film thickness was changed in the range of 0.77 μm was formed under the following conditions.
【００１３】得られたＮｉめっきステンレス鋼板から切
り出された試験片を光沢度試験及び促進劣化試験に供し
た。光沢度試験では、ポータブル表面光沢度計（株式会
社村上色彩研究所製）を使用し、測定角度２０度でめっ
き面の光沢度を測定した。促進劣化試験では、温度６０
℃，相対湿度９０％の恒温恒湿層に試験片を１０日間放
置した後、接触電気抵抗分布測定器（株式会社山崎精機
研究所製）を用い印加電流１０ｍＡ，接触荷重１００ｇ
ｆの条件でめっき面の接触抵抗を測定した。ステンレス
鋼板に対するＮｉめっきとして一般的に使用されている
ウッド浴でＮｉストライクメッキした後、ワット浴で膜
厚３μｍのＮｉめっきを施しためっき材を同じ条件下で
促進劣化試験した後の接触電気抵抗は２５μΩ以下であ
る。そこで、この値２５μΩを基準値とし、２５μΩ未
満の接触抵抗を示した試験片を○，２５μΩ以上の接触
抵抗を示した試験片を×として各めっき材の接触抵抗を
評価した。A test piece cut from the obtained Ni-plated stainless steel sheet was subjected to a glossiness test and an accelerated deterioration test. In the glossiness test, the glossiness of the plated surface was measured at a measurement angle of 20 degrees using a portable surface glossmeter (manufactured by Murakami Color Research Laboratory Co., Ltd.). In the accelerated aging test, a temperature of 60
After leaving the test piece in a thermo-hygrostat at 90 ° C. and a relative humidity of 90% for 10 days, an applied current of 10 mA and a contact load of 100 g were measured using a contact electric resistance distribution measuring device (manufactured by Yamazaki Seiki Laboratories, Inc.).
The contact resistance of the plated surface was measured under the condition of f. Contact electrical resistance after Ni strike plating in a wood bath generally used for Ni plating on stainless steel plates, and then subjected to accelerated deterioration test under the same conditions for a 3 μm-thick Ni plated plating material in a Watt bath Is 25 μΩ or less. Then, using this value of 25 μΩ as a reference value, the contact resistance of each plated material was evaluated by setting a test piece showing a contact resistance of less than 25 μΩ as ○ and a test piece showing a contact resistance of 25 μΩ or more as ×.
【００１４】表１の調査結果にみられるように、無光沢
Ｎｉめっき層のない試験番号１１，１２，１４では、促
進劣化試験後に接触電気抵抗が大きく低下し、電池缶と
しての要求特性を満足していなかった。しかし、比較的
厚く無光沢Ｎｉめっき層を形成した試験番号１３，１
５，１６では、光沢度が低く、電池缶として商品識別性
に乏しいめっき材であった。これに対し、本発明で規定
した膜厚の無光沢Ｎｉめっき層を形成しためっき材で
は、光沢度の低下がなく、促進劣化試験後にも十分に低
い接触抵抗が維持されていた。As can be seen from the survey results in Table 1, in Test Nos. 11, 12, and 14 having no matte Ni plating layer, the contact electric resistance was significantly reduced after the accelerated deterioration test, and the required characteristics as a battery can were satisfied. I didn't. However, Test Nos. 13 and 1 in which a relatively thick matte Ni plating layer was formed
In Nos. 5 and 16, the gloss was low, and the product was poor in product discrimination as a battery can. On the other hand, in the plated material in which the matte Ni plating layer having the film thickness specified in the present invention was formed, the glossiness did not decrease, and a sufficiently low contact resistance was maintained even after the accelerated deterioration test.
【００１５】 [0015]
【００１６】[0016]
【実施例２】表面粗さがＲａ０．０３４〜０．０７１μ
ｍに調整された板厚０．２５ｍｍのＳＵＳ４３０フェラ
イト系ステンレス鋼板をめっき原板として使用し、電解
脱脂，酸洗の前処理を施した後、実施例１と同様な条件
下で膜厚０．２５μｍのＮｉストライクめっき層及び膜
厚０．７〜７．４μｍの光沢Ｎｉめっき層を形成した。
次いで、ワット浴を用いて光沢Ｎｉめっき層の上に膜厚
０〜０．８４μｍの無光沢Ｎｉめっき層を形成した。Example 2 Surface roughness Ra 0.034 to 0.071 μ
A SUS430 ferritic stainless steel sheet having a thickness of 0.25 mm adjusted to m was used as a plating base plate, and subjected to a pretreatment of electrolytic degreasing and pickling, followed by a film thickness of 0.25 μm under the same conditions as in Example 1. And a bright Ni plating layer having a thickness of 0.7 to 7.4 μm.
Next, a matte Ni plating layer having a thickness of 0 to 0.84 μm was formed on the bright Ni plating layer using a Watt bath.
【００１７】得られたＮｉめっきステンレス鋼板の光沢
度及び促進劣化試験後の接触抵抗を実施例１と同様に測
定した。測定結果を示す表２にみられるように、無光沢
Ｎｉめっき層のない試験番号２７，２９，３０では、促
進劣化試験後に接触電気抵抗が大きく低下し、電池缶と
しての要求特性を満足していなかった。しかし、比較的
厚く無光沢Ｎｉめっき層を形成した試験番号２８，３
１，３２では、光沢度が低く、電池缶として商品識別性
に乏しいめっき材であった。これに対し、本発明で規定
した膜厚の無光沢Ｎｉめっき層を形成しためっき材で
は、光沢度の低下がなく、促進劣化試験後にも十分に低
い接触抵抗が維持されていた。The gloss of the obtained Ni-plated stainless steel sheet and the contact resistance after the accelerated deterioration test were measured in the same manner as in Example 1. As shown in Table 2 showing the measurement results, in Test Nos. 27, 29, and 30 without the matte Ni plating layer, the contact electric resistance was significantly reduced after the accelerated deterioration test, and satisfied the required characteristics as a battery can. Did not. However, Test Nos. 28 and 3 in which a relatively thick matte Ni plating layer was formed
In Nos. 1 and 32, the plating material had low gloss and poor product discrimination as a battery can. On the other hand, in the plated material in which the matte Ni plating layer having the film thickness specified in the present invention was formed, the glossiness did not decrease, and a sufficiently low contact resistance was maintained even after the accelerated deterioration test.
【００１８】 [0018]
【００１９】[0019]
【実施例３】オーステナイト結晶粒度番号を６〜１１，
全伸びを４２〜５８％，０．２％耐力を３１０〜５１０
Ｎ／ｍｍ2に調整した表面粗さＲａ：０．０４３μｍ，
板厚０．２５ｍｍのＳＵＳ３０４オーステナイト系ステ
ンレス鋼板をめっき原板として使用し、実施例１と同様
な条件下で膜厚０．２５μｍのＮｉストライクめっき
層，膜厚３．５μｍの光沢Ｎｉめっき層及び膜厚０．４
２μｍの無光沢Ｎｉめっき層を形成した。Example 3 The austenite grain size number was 6 to 11,
Total elongation 42-58%, 0.2% yield strength 310-510
Surface roughness Ra adjusted to N / mm 2 : 0.043 μm,
Using a SUS304 austenitic stainless steel plate having a thickness of 0.25 mm as a plating base plate, under the same conditions as in Example 1, a Ni strike plating layer having a thickness of 0.25 μm, a bright Ni plating layer having a thickness of 3.5 μm and a film Thickness 0.4
A 2 μm matte Ni plating layer was formed.
【００２０】得られためっき材を用い、Ｖ曲げ加工性，
プレス成形性及びカシメ加工性を調査した。Ｖ曲げ加工
性は，８８度Ｖ字金型を用いＮｉめっき面を外側として
曲げ加工し、加工後に曲げ角度９０度が維持されたもの
を○，９０度未満のものを×として評価した。プレス成
形性は、Ｎｉめっき面を外側として外径４０ｍｍ，成形
高さ３０ｍｍの形状に円筒絞り加工した１００個の試験
片につき、缶頭部の表面に発生する形状不良の有無を接
触形状測定計で測定し、形状不良発生率が０個のものを
○，１個でも形状不良が発生したものを×と評価した。
カシメ加工性は，プレス成形された試験片のカシメ部を
観察し、割れや隙間の発生がないものを○，割れ又は隙
間が検出されたものを×と評価した。Using the plating material obtained, V-bending workability,
Press formability and crimpability were investigated. The V-bending workability was evaluated by bending using a 88-degree V-shaped mold with the Ni-plated surface outside, and maintaining a bending angle of 90 degrees after processing as ○, and evaluating less than 90 degrees as x. The press formability was measured by using a contact shape measuring instrument to determine the presence or absence of shape defects that occurred on the surface of the can head for 100 test pieces that had been cylindrically drawn into a shape with an outer diameter of 40 mm and a forming height of 30 mm with the Ni plating surface as the outside. The sample was evaluated as ○ when the shape defect occurrence rate was 0, and as × when at least one shape defect occurred.
The crimping workability was evaluated by observing the crimped portion of the press-formed test piece, and was evaluated as ○ when no crack or gap was generated, and as x when crack or gap was detected.
【００２１】表３の試験結果にみられるように、オース
テナイト結晶粒度番号１１の試験番号４４では、スプリ
ングバックが大きく、Ｖ曲げ加工後に所定の曲げ角度を
維持できなかった。オーステナイト結晶粒度番号が６と
低い試験番号４３では、加工部にクラックの発生が検出
された。これに対し、オーステナイト結晶粒度番号を
６．５〜９．０の範囲に維持するとき、Ｖ曲げ加工後に
良好な曲げ角度が維持された。また、全伸びが５０％以
上，０．２％耐力が５００Ｎ／ｍｍ2以下になると、プ
レス成形性及びカシメ加工性も良好となり、過酷な加工
が施される負極缶として十分使用に耐えることが判っ
た。As can be seen from the test results in Table 3, in test number 44 of austenite grain size number 11, the springback was large, and the predetermined bending angle could not be maintained after V bending. In Test No. 43, in which the austenite grain size number was as low as 6, generation of cracks in the processed portion was detected. On the other hand, when the austenite grain size number was maintained in the range of 6.5 to 9.0, a good bending angle was maintained after the V bending. Further, when the total elongation is 50% or more and the 0.2% proof stress is 500 N / mm 2 or less, the press formability and the crimping workability are improved, and the anode can be sufficiently used as a negative electrode can subjected to severe processing. understood.
【００２２】 [0022]
【００２３】[0023]
【発明の効果】以上に説明したように、本発明の電池缶
は、光沢Ｎｉめっき層を介して薄い無光沢Ｎｉめっき層
を形成したステンレス鋼を負極缶及び正極缶に使用する
ことにより、光沢Ｎｉめっき層に含まれる光沢剤の酸化
分解生成物に起因する接触抵抗の上昇を招くことなく、
低い接触抵抗が長期間にわたって維持され、光沢度の高
いリチウムボタン電池缶のケース材として使用される。As described above, the battery can of the present invention has a high gloss by using a stainless steel having a thin matte Ni plating layer formed on a thin Ni plating layer via a bright Ni plating layer for the negative electrode can and the positive electrode can. Without increasing the contact resistance due to the oxidative decomposition products of the brightener contained in the Ni plating layer,
Low contact resistance is maintained for a long time, and it is used as a case material for a high gloss lithium button battery can.
【図１】 リチウムボタン電池缶の内部構造を示す断面
図FIG. 1 is a cross-sectional view showing the internal structure of a lithium button battery can.
１：正極端子缶 ２：負極端子缶 ３：正極活性物
質 ４：負極活性物質 ５：セパレータ ６：絶縁性パッキング1: Positive terminal can 2: Negative terminal can 3: Positive active material 4: Negative active material 5: Separator 6: Insulating packing
───────────────────────────────────────────────────── フロントページの続き (72)発明者 渡辺 栄次 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 Ｆターム(参考） 4K024 AA03 AB02 AB06 BA04 BB09 BB25 BC01 DA09 DA10 GA02 GA08 GA16 5H011 AA09 CC06 DD18 KK01 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Eiji Watanabe 5th Ishizu Nishicho, Sakai City, Osaka Prefecture F-Term in Nisshin Steel Co., Ltd. Technical Research Laboratory 4K024 AA03 AB02 AB06 BA04 BB09 BB25 BC01 DA09 DA10 GA02 GA08 GA16 5H011 AA09 CC06 DD18 KK01
Claims (2)
されたオーステナイト系ステンレス鋼を基材とし、基材
表面に光沢Ｎｉめっき層を介して層厚０．０１〜０．３
μｍの無光沢Ｎｉめっき層が形成されていることを特徴
とする接触抵抗が低い高光沢リチウムボタン電池負極缶
用片面Ｎｉめっき鋼板。1. An austenitic stainless steel having a surface roughness adjusted to Ra 0.05 μm or less as a base material, and having a thickness of 0.01 to 0.3 through a bright Ni plating layer on the base material surface.
A single-sided Ni-plated steel sheet for a negative electrode can of a high-gloss lithium button battery having a low contact resistance, wherein a matte Ni-plated layer of μm is formed.
されたフェライト系ステンレス鋼を基材とし、基材表面
に光沢Ｎｉめっき層を介して層厚０．０１〜０．３μｍ
の無光沢Ｎｉめっき層が形成されていることを特徴とす
る接触抵抗が低い高光沢リチウムボタン電池正極缶用片
面Ｎｉめっき鋼板。2. A ferrite stainless steel having a surface roughness adjusted to Ra 0.05 μm or less as a base material, and having a thickness of 0.01 to 0.3 μm via a bright Ni plating layer on the base material surface.
A single-sided Ni-plated steel sheet for a high-gloss lithium button battery positive electrode can having a low contact resistance, characterized by having a matte Ni plating layer formed thereon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000094166A JP2001279490A (en) | 2000-03-30 | 2000-03-30 | ONE SIDE Ni PLATED STEEL SHEET HAVING HIGH LUSTER AND REDUCED CONTACT RESISTANCE FOR NEGATIVE AND POSITIVE POLE CANS OF LITHIUM BUTTON CELL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000094166A JP2001279490A (en) | 2000-03-30 | 2000-03-30 | ONE SIDE Ni PLATED STEEL SHEET HAVING HIGH LUSTER AND REDUCED CONTACT RESISTANCE FOR NEGATIVE AND POSITIVE POLE CANS OF LITHIUM BUTTON CELL |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001279490A true JP2001279490A (en) | 2001-10-10 |
Family
ID=18609253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000094166A Withdrawn JP2001279490A (en) | 2000-03-30 | 2000-03-30 | ONE SIDE Ni PLATED STEEL SHEET HAVING HIGH LUSTER AND REDUCED CONTACT RESISTANCE FOR NEGATIVE AND POSITIVE POLE CANS OF LITHIUM BUTTON CELL |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001279490A (en) |
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| JP2003277981A (en) * | 2002-01-18 | 2003-10-02 | Nippon Steel Corp | Ni PLATED STEEL SHEET FOR BATTERY CAN |
| EP1416573A3 (en) * | 2002-10-25 | 2004-08-04 | Samsung SDI Co., Ltd. | Negative electrode for lithium secondary battery and lithium secondary battery comprising same |
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