JP3840430B2 - Surface-treated steel sheet for battery case and battery case - Google Patents
Surface-treated steel sheet for battery case and battery case Download PDFInfo
- Publication number
- JP3840430B2 JP3840430B2 JP2002141080A JP2002141080A JP3840430B2 JP 3840430 B2 JP3840430 B2 JP 3840430B2 JP 2002141080 A JP2002141080 A JP 2002141080A JP 2002141080 A JP2002141080 A JP 2002141080A JP 3840430 B2 JP3840430 B2 JP 3840430B2
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- Prior art keywords
- layer
- iron
- nickel
- plating
- cobalt
- Prior art date
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- Expired - Lifetime
Links
- 229910000831 Steel Inorganic materials 0.000 title claims description 35
- 239000010959 steel Substances 0.000 title claims description 35
- 238000007747 plating Methods 0.000 claims description 79
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 76
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- 238000009792 diffusion process Methods 0.000 claims description 44
- 229910052759 nickel Inorganic materials 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 37
- 229910052742 iron Inorganic materials 0.000 claims description 22
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 22
- 238000000465 moulding Methods 0.000 claims description 20
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 19
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 8
- 239000010410 layer Substances 0.000 description 69
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910000358 iron sulfate Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- -1 polyoxy-ethylene Polymers 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910000655 Killed steel Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- NPURPEXKKDAKIH-UHFFFAOYSA-N iodoimino(oxo)methane Chemical compound IN=C=O NPURPEXKKDAKIH-UHFFFAOYSA-N 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000010409 ironing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 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
- 238000004140 cleaning Methods 0.000 description 1
- CYXIENZYTDFIFC-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Fe].[Co] CYXIENZYTDFIFC-UHFFFAOYSA-N 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000003466 welding 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)
- Other Surface Treatments For Metallic Materials (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Description
【０００１】
【発明の属する技術分野】
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用表面処理鋼板及び該表面処理鋼板を深絞り成形法、ＤＩ成形法又はＤＴＲ成形法によって成形して得られる電池ケースに関する。
【０００２】
【従来の技術】
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−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−スにプレス成形する方法が採用されてきた。
【０００３】
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ているという利点があるからである。
【０００４】
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）。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。
【０００５】
更に、近年、アルカリマンガン電池には、内部抵抗、短絡電流、放電特性などの性能が優れることが要求されている。
【０００６】
【発明が解決すべき課題】
上記したように、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、電池性能の点から、内面の表層がニッケルめっき、あるいは鉄−ニッケル拡散層からなっている。
【０００７】
しかし、缶内面の最表層がニッケルめっき、あるいは鉄−ニッケル拡散層では、電池特性に限界があり、改善が望まれている
本発明はこれらの点に鑑みてなされたものであり、電池性能に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目的とする。
【０００８】
【課題を解決するための手段】
そこで、本発明者等は、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、缶内面の最表層に鉄−ニッケル合金めっき層を有すると、内部抵抗、短絡電流等の電池性能が優れることを見いだして本発明を完成させた。
【００１１】
請求項１に記載の電池ケース用表面処理鋼板は、鋼板からなるめっき原板において、ケース内面に相当する面では、下層として鉄−ニッケル拡散層と、上層としてコバルトを５〜２５重量％含んだ鉄−コバルト−ニッケル合金めっき層を拡散処理することにより形成した鉄を４〜７０重量％含んだ鉄−コバルト−ニッケル拡散層を有し、ケース外面に相当する面では、下層として鉄−ニッケル拡散層、上層としてニッケル層を有することを特徴とする。なお、本発明における重量％は質量％を意味する。
【００１２】
請求項２に記載の電池ケース用表面処理鋼板は、鋼板からなるめっき原板において、ケース内面に相当する面では、鉄−ニッケル拡散層、中間層としてニッケル層と、上層としてコバルトを５〜２５重量％含んだ鉄−コバルト−ニッケル合金めっき層を拡散処理することにより形成した鉄を４〜７０重量％含んだ鉄−コバルト−ニッケル拡散層を有し、ケース外面に相当する面では、下層として鉄−ニッケル拡散層と、上層としてニッケル層を有することを特徴とする。
【００１３】
請求項３に記載の電池ケース用表面処理鋼板は、鋼板からなるめっき原板において、ケース内面に相当する面では、下層として鉄−ニッケル拡散層、上層としてコバルトを５〜２５重量％含んだ鉄−コバルト−ニッケル合金めっき層を拡散処理することにより形成した鉄を４〜７０重量％含んだ鉄−コバルト−ニッケル拡散層を有し、ケース外面に相当する面では、下層として鉄−ニッケル拡散層、上層として鉄−ニッケル合金層を拡散処理した層を有することを特徴とする。
【００１４】
請求項４に記載の電池ケース用表面処理鋼板は、鋼板からなるめっき原板において、ケース内面に相当する面では、下層として、鉄−ニッケル拡散層、中間層としてニッケルめっき層と、上層としてコバルトを５〜２５重量％含んだ鉄−コバルト−ニッケル合金めっき層を拡散処理することにより形成した鉄を４〜７０重量％含んだ鉄−コバルト−ニッケル拡散層を有し、ケース外面に相当する面では、下層として鉄−ニッケル拡散層、中間層としてニッケル層と、上層として鉄−ニッケル合金めっき層を拡散処理した層を有することを特徴とする。
【００１５】
請求項５に記載の電池ケースは、請求項１乃至請求項４のいずれか１項に記載の電池ケース用表面処理鋼板を深絞り成形法、ＤＩ成形法又はＤＴＲ成形法によって成形して得られることを特徴とする。
【００１６】
【発明の実施の形態】
上記した電池ケース及び表面処理鋼板におけるニッケル−鉄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鉄を添加した場合、鉄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鉄含有量が増加する。これらのニッケル−鉄合金めっきだけでなく、更に熱処理することにより、この合金層中の鉄の割合がある一定の範囲で良好な電池性能を示す。単なるニッケル層だけでは、理由は不明であるが電池性能が向上しない。また、鋼板の上に、ニッケルめっきを施した後、熱処理により鉄−ニッケル拡散層を表層に作る場合では、表層の鉄の割合をある一定の範囲に制御することが困難である。
【００１７】
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、優れた電池性能を有する電池ケースが得られる。
【００１８】
ところで、鉄−ニッケル合金めっき層あるいは更に熱処理した後の合金層中の鉄含有量は４．０重量％〜７０重量％の範囲が好適である。鉄含有量が４．０重量％未満では、内部抵抗が高く、好ましくない。７０重量％を超えると耐食性が悪い。
【００１９】
ニッケルめっき厚みは、鉄−ニッケル合金めっきの下層めっきとして行う場合は０〜３μｍの範囲が好ましい。３μｍを超えても、特性に影響ないが、厚すぎて不経済となる。缶外面側がニッケルめっきの単層の構成となる場合では、１〜４μｍが好ましい。１μｍ未満では、耐食性が悪い。４μｍを超えても、耐食性はほとんど向上せず、不経済である。
【００２０】
本発明の鉄−ニッケル合金めっきでは、０．２〜３μｍの範囲が望ましい。０．２μｍ未満では、めっき層、あるいは拡散層が薄くて電池性能は悪い。一方、３μｍを超えても、電池性能はほとんど変わらないが、厚すぎて不経済である。
【００２１】
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。
【００２２】
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、ニッケルめっきを片面あるいは両面に行っても良い。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。ニッケルめっきでは、無光沢めっき、半光沢めっきが良い。このニッケルめっき後、あるいはニッケルめっきを施さないで、鉄−ニッケル合金めっきを行う。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。鉄−ニッケルめっきでは、無光沢めっき、半光沢めっきが良い。
【００２３】
この鉄−ニッケル合金めっき後、熱処理により表層にニッケル−鉄拡散層を形成しても良い。鉄−ニッケル合金めっき層を熱処理した後の合金層中の鉄含有量は４．０重量％〜７０重量％の範囲が好適である。鉄含有量が４．０重量％未満では、内部抵抗が高く、好ましくない。７０重量％を超えると、耐食性が悪い。この鉄−ニッケル合金めっき層は、更にコバルトを５〜２５重量％含んでも良い。
【００２４】
この際、下層にも、下地の鉄とニッケルめっきによる鉄−ニッケル拡散層ができるが、このニッケルめっき層は全て鉄−ニッケル拡散層にしても良いし、１部残存しても良い。この目的のためには、箱型焼鈍法による熱処理では、４５０〜６５０℃の温度で４〜１５時間、連続焼鈍法では、６００〜８５０℃の温度で、０．５〜３分程度の熱処理が好ましい。
【００２５】
【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。
【００２６】
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。また、板厚０．２５ｍｍならびに０．４ｍｍの冷間圧延後の極低炭素アルミキルド鋼板をめっき原板とした。両めっき原板の鋼化学組成は、共に、下記の通りである。
【００２７】
Ｃ：０．０４％（％は重量％、以下同じ）
Ｓｉ：０．０１％
Ｍｎ：０．２２％、
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を行う。
【００２８】
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。
【００２９】
浴組成
硫酸ニッケル（NiSO４・6H２O） 300 g/L
塩化ニッケル（NiCl２・6H２O） 45 g/L
硼酸 （H３BO３） 30 g/L
浴pH：4（硫酸で調整)
撹拌：空気撹拌
浴温度： 60 ℃
アノ−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。
【００３０】
また、半光沢ニッケルめっきについては、下記のめっき浴を使う。この半光沢ニッケルめっきは、最初の無光沢ニッケルめっきの替わりに実施しても良い。
【００３１】
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。
【００３２】
浴組成
硫酸ニッケル（NiSO４・6H２O） 300 g/L
塩化ニッケル（NiCl２・6H２O） 45 g/L
硼酸 （H３BO３） 30 g/L
不飽和アルコールのポリオキシーエチレン付加物 3.0 g/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−ド：Ｓペレット（ＩＮＣＯ社製商品名、球状）をチタンバスケットに
装填してポリプロピレン製バッグで覆ったもの。
【００３３】
更に、鉄−ニッケル合金めっきを行った。
【００３４】
３）鉄−ニッケル合金めっき
硫酸ニッケル浴に硫酸鉄を適宜添加してニッケルめっき層中に鉄を含有させた。
【００３５】
浴組成
硫酸ニッケル（NiSO４・6H２O） 320 g/L
塩化ニッケル（NiCl２・6H２O） 20 g/L
硫酸鉄 （FeSO４・6H２O） （適宜）
硼酸 （H３BO３） 30 g/L
浴pH： 4（硫酸で調整)
撹拌：空気撹拌
浴温度： 60 ℃
アノ−ド：Ｓペレット（ＩＮＣＯ社製商品名、球状）をチタンバスケットに
装填してポリプロピレン製バッグで覆ったもの。
【００３６】
また、更にコバルトを含む場合では、硫酸コバルトをこのめっき浴に適宜添加すればよい。
【００３７】
上記の条件で、硫酸鉄添加量および電解時間を変えて、めっき皮膜中の鉄含有量、めっき厚みを変化させた。これらのめっき条件については、表１に示す。
【００３８】
鉄−ニッケル合金めっき後、熱処理により、鉄−ニッケル合金層に拡散処理を施しても良い。拡散処理条件は、非酸化性雰囲気あるいは還元性雰囲気が好ましく、例えば水素６．５％、残部窒素ガスの非酸化性雰囲気中で行っても良い。この拡散処理は、箱型焼鈍炉、あるいは連続焼鈍炉などの公知の設備を使っても良い。なお、熱処理条件は、表１に示す。
【００３９】
（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。ＤＩ成形法は、実施例１〜６、比較例１と比較例４の表面処理鋼板を用いた。
【００４０】
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。ＤＴＲ成形法は、実施例７〜１０と比較例２の表面処理鋼板を用いた。
【００４１】
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。深絞り成形法は、実施例１１〜１４と比較例３の表面処理鋼板を用いた。
【００４２】
上記のように、作成した電池ケースを用いてアルカリマンガン電池を作成し、特性を評価した。評価結果を表１に示す。
【００４３】
［内部抵抗（ＩＲ）の評価］
作製した電池を８０℃で３日経時後、交流インピーダンス法で内部抵抗（ｍΩ）を測定した。
【００４４】
［短絡電流（ＳＣＣ）の評価］
作製した電池を８０℃で３日経時後、該電池に電流計を接続して閉回路を設け、電池の電流値を測定し、これを短絡電流とした。
【００４５】
［放電特性］
作製した電池を８０℃で３日経時後、該電池に２Ωの抵抗を使用して閉回路を作成し、電圧が０．９Ｖに達するまでの経時時間を測定した。
【００４６】
【表１】
【発明の効果】
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内面側の最表層に鉄−ニッケル合金めっき層あるいは熱処理した拡散処理層を有する電池ケースは、従来のような電池ケース内面のニッケルめっき層あるいはニッケル層を有する電池ケースと比べて電池性能（内部抵抗、短絡電流、放電特性）が良好である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a container enclosing an alkaline solution, more specifically, a surface-treated steel sheet for battery outer cases such as alkaline manganese batteries and nickel-cadmium batteries, and the surface-treated steel sheet by a deep drawing method, DI molding method or DTR molding method. The present invention relates to a battery case obtained by molding.
[0002]
[Prior art]
Conventionally, a battery case enclosing a strong alkaline solution such as an alkaline manganese battery or a nickel-cadmium battery is formed by pressing a cold-rolled steel strip into a battery case, followed by barrel plating or using a nickel-plated steel strip as a battery case. A method of press molding in a mold has been adopted.
[0003]
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.
[0004]
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.
[0005]
Furthermore, in recent years, alkaline manganese batteries are required to have excellent performance such as internal resistance, short-circuit current, and discharge characteristics.
[0006]
[Problems to be Solved by the Invention]
As described above, in recent years, a battery case produced by a deep drawing method, DI molding method or DTR molding method has an inner surface layer made of nickel plating or an iron-nickel diffusion layer from the viewpoint of battery performance.
[0007]
However, if the outermost layer on the inner surface of the can is nickel-plated or an iron-nickel diffusion layer, the battery characteristics are limited, and the present invention, which is desired to be improved, has been made in view of these points. An object is to provide an excellent battery case and a surface-treated steel sheet that can be suitably used for producing the battery case.
[0008]
[Means for Solving the Problems]
Therefore, from such a viewpoint, the inventors of the present invention have a battery case produced by a deep drawing method, a DI molding method and a DTR molding method, and the inner surface of the can has an iron-nickel alloy plating layer. The present invention was completed by finding that the battery performance such as resistance and short circuit current was excellent.
[0011]
The surface-treated steel sheet for a battery case according to claim 1 is an iron-nickel diffusion layer as a lower layer and an iron containing 5 to 25% by weight of cobalt as an upper layer on a surface corresponding to the inner surface of the plating base plate made of a steel plate . -An iron- cobalt- nickel diffusion layer containing 4 to 70 wt% of iron formed by diffusion treatment of a cobalt- nickel alloy plating layer, and an iron-nickel diffusion layer as a lower layer on the surface corresponding to the outer surface of the case And having a nickel layer as an upper layer. In the present invention, “% by weight” means “% by mass”.
[0012]
The surface-treated steel sheet for a battery case according to claim 2 is a plating base sheet made of a steel sheet, and has an iron-nickel diffusion layer, a nickel layer as an intermediate layer, and cobalt as an upper layer in an amount corresponding to 5 to 25 wt. % inclusive of iron - cobalt - iron 4 to 70 wt% inclusive iron formed by diffusing processing nickel alloy plating layer - cobalt - has a nickel diffusion layer, the surface corresponding to the case outer surface, iron as the lower layer -It has a nickel diffusion layer and a nickel layer as an upper layer.
[0013]
The surface-treated steel sheet for a battery case according to claim 3 is a plating original sheet made of a steel sheet, and on the surface corresponding to the inner surface of the case, an iron-nickel diffusion layer as a lower layer and an iron containing 5 to 25% by weight of cobalt as an upper layer It has an iron- cobalt- nickel diffusion layer containing 4 to 70% by weight of iron formed by diffusion treatment of a cobalt- nickel alloy plating layer, and on the surface corresponding to the outer surface of the case, an iron-nickel diffusion layer as a lower layer, It is characterized by having a layer obtained by diffusing an iron-nickel alloy layer as an upper layer.
[0014]
The surface-treated steel sheet for a battery case according to claim 4 is a plating base plate made of a steel sheet, and on the surface corresponding to the inner surface of the case, an iron-nickel diffusion layer as a lower layer, a nickel plating layer as an intermediate layer, and cobalt as an upper layer. In the surface corresponding to the outer surface of the case, it has an iron- cobalt- nickel diffusion layer containing 4 to 70% by weight of iron formed by diffusion treatment of an iron- cobalt- nickel alloy plating layer containing 5 to 25% by weight. The lower layer has an iron-nickel diffusion layer, the intermediate layer has a nickel layer, and the upper layer has a diffusion-treated layer of an iron-nickel alloy plating layer.
[0015]
The battery case according to claim 5 is obtained by forming the surface-treated steel sheet for battery case according to any one of claims 1 to 4 by a deep drawing method, a DI forming method, or a DTR forming method. It is characterized by that.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The generation of nickel-iron alloy plating in the above battery case and surface-treated steel sheet will be described. When iron sulfate is added to the Watt bath and sulfamic acid bath, iron is co-deposited with nickel, and as a result, the eutectoid plating layer is The iron content in the plating film increases. In addition to these nickel-iron alloy platings, by further heat treatment, good battery performance is exhibited within a certain range of the ratio of iron in the alloy layer. The mere nickel layer alone does not improve the battery performance, for unknown reasons. In addition, when an iron-nickel diffusion layer is formed as a surface layer by heat treatment after nickel plating on a steel plate, it is difficult to control the ratio of iron in the surface layer within a certain range.
[0017]
Note that the present invention can provide a battery case having excellent battery performance without depending on a battery case molding method, for example, a deep drawing method, a DI molding method, or a DTR molding method.
[0018]
By the way, the iron content in the iron-nickel alloy plating layer or the alloy layer after further heat treatment is preferably in the range of 4.0 wt% to 70 wt%. If the iron content is less than 4.0% by weight, the internal resistance is high, which is not preferable. If it exceeds 70% by weight, the corrosion resistance is poor.
[0019]
The nickel plating thickness is preferably in the range of 0 to 3 μm when the lower plating of iron-nickel alloy plating is performed. Even if it exceeds 3 μm, the properties are not affected, but it is too thick and uneconomical. In the case where the outer surface side of the can has a single layer structure of nickel plating, 1 to 4 μm is preferable. If it is less than 1 μm, the corrosion resistance is poor. Even if it exceeds 4 μm, the corrosion resistance is hardly improved, which is uneconomical.
[0020]
In the iron-nickel alloy plating of the present invention, a range of 0.2 to 3 μm is desirable. If the thickness is less than 0.2 μm, the plating layer or the diffusion layer is thin and the battery performance is poor. On the other hand, even if it exceeds 3 μm, the battery performance is hardly changed, but it is too thick and uneconomical.
[0021]
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.
[0022]
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. Thereafter, nickel plating may be performed on one side or both sides using this plating original plate. The plating bath may be either a known sulfuric acid bath or a sulfamic acid bath, but a sulfuric acid bath that is relatively easy to manage is suitable. For nickel plating, matte plating and semi-gloss plating are good. Iron-nickel alloy plating is performed after this nickel plating or without nickel plating. 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. For iron-nickel plating, matte plating and semi-gloss plating are good.
[0023]
After the iron-nickel alloy plating, a nickel-iron diffusion layer may be formed on the surface layer by heat treatment. The iron content in the alloy layer after heat-treating the iron-nickel alloy plating layer is preferably in the range of 4.0 wt% to 70 wt%. If the iron content is less than 4.0% by weight, the internal resistance is high, which is not preferable. If it exceeds 70% by weight, the corrosion resistance is poor. This iron-nickel alloy plating layer may further contain 5 to 25% by weight of cobalt.
[0024]
At this time, an iron-nickel diffusion layer formed by underlying iron and nickel plating is also formed in the lower layer, but all of this nickel plating layer may be an iron-nickel diffusion layer, or one part may remain. For this purpose, the heat treatment by the box-type annealing method is performed at a temperature of 450 to 650 ° C. for 4 to 15 hours, and the continuous annealing method is performed at a temperature of 600 to 850 ° C. for about 0.5 to 3 minutes. preferable.
[0025]
【Example】
The present invention will be further specifically described with reference to the following examples.
[0026]
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. Further, an ultra-low carbon aluminum killed steel sheet after cold rolling with a plate thickness of 0.25 mm and 0.4 mm was used as a plating original sheet. The steel chemical composition of both plating original plates is as follows.
[0027]
C: 0.04% (% is% by weight, the same applies hereinafter)
Si: 0.01%
Mn: 0.22%,
P: 0.012%
S: 0.006%
Al: 0.0.48%
N: 0.0025%
After performing the pretreatment after alkaline electrolytic degreasing, water washing, sulfuric acid immersion, and water washing, the above-mentioned plating original plate is subjected to normal matte nickel plating.
[0028]
1) Matte nickel plating Matte nickel plating was performed using the following nickel sulfate bath.
[0029]
Bath composition Nickel sulfate (NiSO4 ・ 6H2O) 300 g / L
Nickel chloride (NiCl2 · 6H2O) 45 g / L
Boric acid (H3BO3) 30 g / L
Bath pH: 4 (adjusted with sulfuric acid)
Stirring: Air stirring bath temperature: 60 ° C
Anod: S pellets (trade name, manufactured by INCO, spherical shape) loaded in a titanium basket and covered with a polyprolene bag.
[0030]
For semi-bright nickel plating, the following plating bath is used. This semi-bright nickel plating may be performed instead of the initial matte nickel plating.
[0031]
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.
[0032]
Bath composition Nickel sulfate (NiSO4 ・ 6H2O) 300 g / L
Nickel chloride (NiCl2 · 6H2O) 45 g / L
Boric acid (H3BO3) 30 g / L
Polyoxyethylene adduct of unsaturated alcohol 3.0 g / L
Unsaturated carboxylic acid formaldehyde 3.0g / L
Bath pH: 4 (adjusted with sulfuric acid)
Stirring: Air stirring bath temperature: 60 ° C
Anod: S pellets (trade name, manufactured by INCO, spherical) are loaded into a titanium basket and covered with a polypropylene bag.
[0033]
Furthermore, iron-nickel alloy plating was performed.
[0034]
3) Iron-nickel alloy plating Iron sulfate was appropriately added to a nickel sulfate bath to contain iron in the nickel plating layer.
[0035]
Bath composition Nickel sulfate (NiSO4 ・ 6H2O) 320 g / L
Nickel chloride (NiCl2 ・ 6H2O) 20 g / L
Iron sulfate (FeSO4 · 6H2O) (as appropriate)
Boric acid (H3BO3) 30 g / L
Bath pH: 4 (adjusted with sulfuric acid)
Stirring: Air stirring bath temperature: 60 ° C
Anod: S pellets (trade name, manufactured by INCO, spherical) are loaded into a titanium basket and covered with a polypropylene bag.
[0036]
Further, in the case where cobalt is further contained, cobalt sulfate may be appropriately added to the plating bath.
[0037]
Under the above conditions, the iron content and plating thickness in the plating film were changed by changing the iron sulfate addition amount and the electrolysis time. These plating conditions are shown in Table 1.
[0038]
After the iron-nickel alloy plating, the iron-nickel alloy layer may be subjected to a diffusion treatment by heat treatment. The diffusion treatment condition is preferably a non-oxidizing atmosphere or a reducing atmosphere. For example, the diffusion treatment may be performed in a non-oxidizing atmosphere of 6.5% hydrogen and the remaining nitrogen gas. For this diffusion treatment, a known facility such as a box annealing furnace or a continuous annealing furnace may be used. The heat treatment conditions are shown in Table 1.
[0039]
(Battery case fabrication)
The battery case is produced by DI molding using the above-mentioned plated steel plate with a thickness of 0.4 mm, cupping from a blank diameter of 41 mm to a diameter of 20.5 mm, and then using a DI molding machine to perform redo and two-stage ironing. 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. As the DI forming method, the surface-treated steel sheets of Examples 1 to 6, Comparative Example 1 and Comparative Example 4 were used.
[0040]
In addition, the battery case by the DTR molding method is manufactured by using a plated steel sheet having a thickness of 0.25 mm, punching out to a blank diameter of 58 mm, drawing several times, redrawing and forming 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. The surface-treated steel sheets of Examples 7 to 10 and Comparative Example 2 were used for the DTR forming method.
[0041]
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. For the deep drawing method, the surface-treated steel sheets of Examples 11 to 14 and Comparative Example 3 were used.
[0042]
As described above, an alkaline manganese battery was prepared using the prepared battery case, and the characteristics were evaluated. The evaluation results are shown in Table 1.
[0043]
[Evaluation of internal resistance (IR)]
The produced battery was aged at 80 ° C. for 3 days, and then the internal resistance (mΩ) was measured by an AC impedance method.
[0044]
[Evaluation of short circuit current (SCC)]
The produced battery was aged at 80 ° C. for 3 days, an ammeter was connected to the battery, a closed circuit was provided, the current value of the battery was measured, and this was used as a short-circuit current.
[0045]
[Discharge characteristics]
After the produced battery was aged for 3 days at 80 ° C., a closed circuit was created using a resistance of 2Ω for the battery, and the elapsed time until the voltage reached 0.9 V was measured.
[0046]
[Table 1]
【The invention's effect】
A battery case having an iron-nickel alloy plating layer or a heat-treated diffusion treatment layer on the innermost surface layer obtained by molding by a deep drawing method, DI molding method or DTR molding method is a conventional battery case inner surface. Battery performance (internal resistance, short-circuit current, discharge characteristics) is better than a battery case having a nickel plating layer or nickel layer.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002141080A JP3840430B2 (en) | 2002-05-16 | 2002-05-16 | Surface-treated steel sheet for battery case and battery case |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002141080A JP3840430B2 (en) | 2002-05-16 | 2002-05-16 | Surface-treated steel sheet for battery case and battery case |
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| Publication Number | Publication Date |
|---|---|
| JP2003328158A JP2003328158A (en) | 2003-11-19 |
| JP3840430B2 true JP3840430B2 (en) | 2006-11-01 |
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| JP2002141080A Expired - Lifetime JP3840430B2 (en) | 2002-05-16 | 2002-05-16 | Surface-treated steel sheet for battery case and battery case |
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| EP2339038B8 (en) | 2006-07-21 | 2017-01-11 | Kabushiki Kaisha Kobe Seiko Sho | Copper alloy sheet for electric and electronic part |
| JP6394847B1 (en) * | 2017-03-02 | 2018-09-26 | 新日鐵住金株式会社 | Surface-treated steel sheet |
| JP6669321B2 (en) | 2018-02-14 | 2020-03-18 | 日本製鉄株式会社 | Surface-treated steel sheet for battery container and method for producing surface-treated steel sheet for battery container |
| WO2020009213A1 (en) * | 2018-07-06 | 2020-01-09 | 日本製鉄株式会社 | Surface-treated steel sheet and method for manufacturing surface-treated steel sheet |
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