JP2009167486A - Ferritic stainless steel for battery component member - Google Patents
Ferritic stainless steel for battery component member Download PDFInfo
- Publication number
- JP2009167486A JP2009167486A JP2008008597A JP2008008597A JP2009167486A JP 2009167486 A JP2009167486 A JP 2009167486A JP 2008008597 A JP2008008597 A JP 2008008597A JP 2008008597 A JP2008008597 A JP 2008008597A JP 2009167486 A JP2009167486 A JP 2009167486A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- battery
- corrosion resistance
- less
- ferritic stainless
- 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.)
- Pending
Links
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 239000002344 surface layer Substances 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract 2
- 239000000470 constituent Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 3
- 239000012535 impurity Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 6
- 239000013585 weight reducing agent Substances 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000002161 passivation Methods 0.000 abstract description 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract 1
- 229910052758 niobium Inorganic materials 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 description 33
- 238000005260 corrosion Methods 0.000 description 33
- 239000010935 stainless steel Substances 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910018502 Ni—H Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
Abstract
Description
本発明は、Ｌｉイオン二次電池などの非水系電解液電池およびＮｉ−Ｈ水系電解液電池などの構成部品である電池ケースおよび集電体などに適用可能なフェライト系ステンレス鋼に関する。 The present invention relates to a ferritic stainless steel applicable to battery cases and current collectors that are constituent parts of non-aqueous electrolyte batteries such as Li-ion secondary batteries and Ni-H aqueous electrolyte batteries.
近年、環境保護のためにガソリンなど化石燃料に替えて、次世代エネルギーの開発が進められている。
自動車業界においては電気自動車やハイブリッド自動車などの導入はその最たるものであり、モーター駆動用電池の開発が鋭意行われている。さらに携帯やパ−ソナルコンピューターの普及にともない軽量でかつ長時間の電力供給可能なバッテリーの開発が進められている。さらに、家庭用の電気に対しても、災害時の非常用電源として大容量バッテリーの開発が進められている。
In recent years, in order to protect the environment, development of next-generation energy has been promoted in place of fossil fuels such as gasoline.
In the automobile industry, the introduction of electric vehicles, hybrid vehicles, etc. is the best, and development of batteries for driving motors is eagerly underway. Furthermore, with the spread of mobile phones and personal computers, development of lightweight batteries that can supply power for a long time is underway. In addition, for household electricity, development of large-capacity batteries as an emergency power source in the event of a disaster is underway.
これらのバッテリーにおいては高出力でかつ高エネルギー密度のものが望ましく、従来の鉛蓄電池やＮｉ−Ｈなど水系電解液電池から、Ｌｉイオン電池に代表される非水電解液系電池の開発が進められている。
これらの高容量バッテリーにおいては安全性、軽量化、高性能化が求められている。しかし、特に非水電解液系電池の場合には、電池内での短絡や外部衝撃が起こると電解液が燃焼し、発火する可能性がある。
従来、電池ケースにはＡｌやＮｉめっき鋼板などの金属やラミネート樹脂などが用いられていたが、上記の問題に対応するために金属材料を厚肉化して頑丈にすることは重量が増えるため、本来の軽量化の目的に反する。また樹脂製ケースでは強度不足となる。
These high-capacity batteries are required to have safety, weight reduction and high performance. However, particularly in the case of a non-aqueous electrolyte battery, if a short circuit or an external impact occurs in the battery, the electrolyte may burn and ignite.
Conventionally, metals such as Al and Ni-plated steel sheets and laminate resins have been used for battery cases, but increasing the weight to make metal materials thicker and more rugged to address the above problems increases the weight. Contrary to the original purpose of weight reduction. In addition, the resin case is insufficient in strength.
電池性能向上のために電池全体の容量を大きくしようとすると、電池体積が大きくなるために自動車においては設置スぺースがとられ非効率的となる。さらに車両重量が全体として重くなるために燃費も低下する。また、増えた分だけ電池のコストが増大するという問題も生じる。 If an attempt is made to increase the capacity of the entire battery in order to improve battery performance, the volume of the battery will increase, resulting in an inefficient installation space in an automobile. Furthermore, since the vehicle weight becomes heavier as a whole, fuel consumption is also reduced. There is also a problem that the cost of the battery increases by the increased amount.
集電体としては活物質が塗布された金属箔が用いられ、正極にはＡｌ箔、負極にはＣｕ箔が用いられる。将来的な高出力化に対しては、今後、電池の高電圧化が考えられ、集電体としては高電位環境で耐食性を有する材料が望まれる。現行のＡｌやＣｕでは電位付加環境における電解液中で耐食性を維持できないことも考えられる。特に負極のＣｕについて充電時にＣｕが溶出し、放電時に再析出すると、スパークなどの問題が生じる。 As the current collector, a metal foil coated with an active material is used, an Al foil is used for the positive electrode, and a Cu foil is used for the negative electrode. For future high output, it is conceivable to increase the voltage of the battery in the future, and a material having corrosion resistance in a high potential environment is desired as a current collector. It is also conceivable that current Al and Cu cannot maintain corrosion resistance in an electrolytic solution in a potential application environment. In particular, when Cu of the negative electrode elutes during charging and re-deposits during discharging, problems such as sparking occur.
そこで、本発明では、これらの問題を解消すべく案出されたものであり、今後の大容量バッテリーの安全性向上、軽量化、高性能化に寄与することが可能な電池構成部材を提供することを目的とする。 Therefore, the present invention has been devised to solve these problems, and provides a battery component that can contribute to improving the safety, weight and performance of future large-capacity batteries. For the purpose.
本発明者らはこれらの電池用部材として耐食性および強度を有するステンレス鋼の適用性を検討した。基材の材質が特定されＣｒリッチの不働態皮膜が基材表面に形成されているステンレス鋼を使用することにより、それらの問題が解決可能となった。 The present inventors examined the applicability of stainless steel having corrosion resistance and strength as these battery members. These problems can be solved by using stainless steel in which the material of the substrate is specified and a Cr-rich passive film is formed on the surface of the substrate.
本発明はその目的を達成するために、質量％においてＣｒ：１６．０〜３２．０％、Ｃ：０．０１５％以下、Ｓｉ：０．５ ％以下、Ｍｎ：２．０％以下を有し、あるいはさらにＭｏ：０．５〜２．０％、Ｎｉ：２．０％以下、Ｃｕ：
２．０％の１種又は２種以上、あるいはさらにＮｂ：０．１〜０．８％、Ｔｉ：０．０５〜０．４％、Ａｌ：０．０１〜０．５％，Ｂ：０．３％以下の1種又は２種以上を含有するフェライト系ステンレス鋼であり、表層に組成比でＣｒ／（Ｃｒ＋Ｆｅ）＞０．２でかつ４ｎｍ以下の不動態皮膜を有する電池構成部材を提供する。
In order to achieve the object, the present invention has Cr: 16.0 to 32.0%, C: 0.015% or less, Si: 0.5% or less, and Mn: 2.0% or less in mass%. Or Mo: 0.5 to 2.0%, Ni: 2.0% or less, Cu:
One or more of 2.0%, or Nb: 0.1 to 0.8%, Ti: 0.05 to 0.4%, Al: 0.01 to 0.5%, B: 0 Provided is a battery constituent member which is a ferritic stainless steel containing one or more of 3% or less, and has a passive film with a composition ratio of Cr / (Cr + Fe)> 0.2 and 4 nm or less on the surface layer. To do.
本発明によれば、今後の大容量バッテリーの安全性向上、軽量化、高性能化に寄与することが可能な電池構成部材を提供することを目的とする。 According to the present invention, it is an object to provide a battery constituent member that can contribute to the improvement of safety, weight reduction, and high performance of future large-capacity batteries.
ステンレス鋼は表面の不動態皮膜によって優れた耐食性が維持できる。特に電位がかかった状態で不動態を維持できるのはステンレス鋼の特徴である。非水溶液環境においては腐食に対して必要な酸素が供給されないことからより一層の耐食性が期待される。ステンレス鋼の耐食性は構成成分の影響を受けるとともに、表面の不動態皮膜の組成および厚みにより異なる。本発明の組成および不動態皮膜を有するものは電池構成部材として適切な耐食性を有することができる。 Stainless steel can maintain excellent corrosion resistance due to the passive film on the surface. In particular, it is a characteristic of stainless steel that it can maintain a passive state when an electric potential is applied. In a non-aqueous solution environment, oxygen required for corrosion is not supplied, so that further corrosion resistance is expected. The corrosion resistance of stainless steel is affected by the components and varies depending on the composition and thickness of the passive film on the surface. Those having the composition and passive film of the present invention can have appropriate corrosion resistance as a battery component.
不動態皮膜の自己生成が行なわれない非水溶液環境で良好な耐食性を得るためには、ステンレス鋼の表層に組成比でＣｒ／（Ｃｒ＋Ｆｅ）＞０．２でかつ厚さ４ｎｍ以下の不動態皮膜を生成させることが必要である。
ステンレス鋼表面の不動態皮膜は非晶質のＣｒの酸化物および水和物よりなる。Ｃｒの組成比が高いほどＦｅの溶出にともなう腐食が起こりにくく耐食性には有利であることから、電池環境における耐食性を維持するための組成としてＣｒ／（Ｃｒ＋Ｆｅ）＞０．２とした。
また不動態皮膜の耐食性は薄くて緻密なものほど優れることから、その不動態皮膜厚みを４ｎｍ以下とした。
不動態皮膜は通常の腐食環境においてもステンレス鋼の表面に自然に生成するものであるが、空気中の酸素をとりこむと厚く、ポーラスな皮膜が形成されやすい。したがって、酸化性の酸による酸洗処理によって、Ｃｒ組成比が高く、緻密な皮膜が得られる。
光輝焼鈍などの還元雰囲気下での焼鈍では、Ｃｒ組成比は高くなるものの粗で欠陥の多い皮膜となり、電池内部のような過酷な腐食環境では十分な耐食性は得られない。また、酸洗に使用する酸が塩酸など非酸化性で再不動態化性のない酸である場合には、Ｃｒの低い皮膜となるため、耐食性は劣る。
In order to obtain good corrosion resistance in a non-aqueous solution environment in which a passive film is not self-generated, a passive film having a composition ratio of Cr / (Cr + Fe)> 0.2 and a thickness of 4 nm or less is formed on a stainless steel surface layer. Must be generated.
The passive film on the stainless steel surface consists of amorphous Cr oxide and hydrate. Since the higher the Cr composition ratio, the less likely the corrosion due to elution of Fe is, and the better the corrosion resistance, Cr / (Cr + Fe)> 0.2 is set as the composition for maintaining the corrosion resistance in the battery environment.
Further, since the thinner and more precise the corrosion resistance of the passive film is, the thickness of the passive film is set to 4 nm or less.
The passive film is naturally formed on the surface of the stainless steel even in a normal corrosive environment, but is thick and easily forms a porous film when oxygen in the air is taken in. Therefore, a pickling treatment with an oxidizing acid provides a dense film with a high Cr composition ratio.
In annealing under a reducing atmosphere such as bright annealing, although the Cr composition ratio is high, the film is rough and has many defects, and sufficient corrosion resistance cannot be obtained in a severe corrosive environment such as the inside of the battery. In addition, when the acid used for pickling is a non-oxidizing acid such as hydrochloric acid and has no repassivation property, the corrosion resistance is inferior because the film is low in Cr.
電池ケースにＡｌを用いる場合には負極端子と接続される場合があり、ケース自身にも充放電の電位がかかる。したがって、電解液に対する耐食性はもちろん高電位環境における耐食性が要求される。本発明のフェライト系ステンレス鋼はそれらの腐食環境に耐えうる。 When Al is used for the battery case, it may be connected to a negative electrode terminal, and the case itself is charged and discharged. Therefore, not only the corrosion resistance to the electrolytic solution but also the corrosion resistance in a high potential environment is required. The ferritic stainless steel of the present invention can withstand these corrosive environments.
正極集電体においても貴な電位がかかる環境に曝されるが本発明のフェライト系ステンレス鋼はそれらの腐食環境に耐えることができる。 Although the positive electrode current collector is also exposed to an environment in which a noble potential is applied, the ferritic stainless steel of the present invention can withstand such a corrosive environment.
一方、負極集電体においては耐食性に劣る金属であれば充電時に金属が溶出し、放電時に集電体表面に析出する問題が生じるが、本発明のフェライト系ステンレス鋼は耐食性に優れるためにそれらの問題がない。 On the other hand, in the negative electrode current collector, if the metal is inferior in corrosion resistance, there will be a problem that the metal elutes during charging and precipitates on the surface of the current collector during discharging, but the ferritic stainless steel of the present invention is excellent in corrosion resistance. There is no problem.
Ｃｒは電池環境におけるステンレス鋼としての耐食性を維持するために最も重要な元素である。耐食性を備えるためには１６．０％の含有が必要であるが、Ｃｒ量が高くなると、靭性や加工性の低下を招くためＣｒ含有量の上限を３２．０％とする。 Cr is the most important element for maintaining the corrosion resistance as stainless steel in the battery environment. In order to provide corrosion resistance, the content of 16.0% is necessary. However, if the Cr content is increased, the toughness and workability are reduced, so the upper limit of the Cr content is 32.0%.
Ｃは炭化物を形成し、それが最終焼鈍での再結晶フェライトのランダム化の再結晶核として働く。しかしＣは冷延焼鈍後の強度を上昇させる元素であり、あまり高いと延性の低下を招くため、０．０１５％以下とした。 C forms carbides, which serve as recrystallization nuclei for randomization of recrystallized ferrite in the final annealing. However, C is an element that increases the strength after cold rolling annealing, and if it is too high, the ductility is lowered.
Ｓｉは通常脱酸の目的のために使用するが、固溶強化能が高く、あまりその含有量が多いと材質が硬化し延性の低下を招くので、０．５％以下とした。 Si is usually used for the purpose of deoxidation, but its solid solution strengthening ability is high, and if its content is too large, the material is hardened and the ductility is lowered, so the content was made 0.5% or less.
Ｍｎはオーステナイト形成元素であり、固溶強化能が小さく材質への悪影響が少ない。しかし、含有量が多いと溶製時にＭｎヒュームが生成する等、製造性が低下するので、望ましくは成分範囲を２．０%以下とした。 Mn is an austenite-forming element, has a low solid solution strengthening ability and has little adverse effect on the material. However, if the content is large, Mn fumes are generated during melting, and the manufacturability is lowered. Therefore, the component range is desirably set to 2.0% or less.
Ｍｏは耐食性を改善するのに有効な元素である。０．５％以上でその作用は認められる。しかし、過度の添加は高温での固溶強化や動的再結晶の遅滞により、熱間加工性の低下をもたらすとともにコストの上昇を招くので０．５〜２．０％とした。 Mo is an element effective for improving the corrosion resistance. The effect is recognized at 0.5% or more. However, excessive addition causes a reduction in hot workability and an increase in cost due to solid solution strengthening at a high temperature and delay of dynamic recrystallization, so the content is set to 0.5 to 2.0%.
Ｎｉはオーステナイト形成元素であり、２．０％を越える添加は硬質化やコスト上昇を招くため、２．０％を上限とした。 Ni is an austenite forming element, and addition over 2.0% leads to hardening and cost increase, so 2.0% was made the upper limit.
Ｃｕはステンレス鋼の耐食性を向上させるのに有効な元素であるが、過度の添加は熱間加工性や耐食性を低下させるので２．０％以下とした。 Cu is an element effective for improving the corrosion resistance of stainless steel, but excessive addition reduces the hot workability and corrosion resistance, so it was made 2.0% or less.
ＮｂはＣ，Ｎを固定し、耐衝撃特性や二次加工性を向上させる元素であり、電池ケースなどの加工に対しては加工性を向上させる効果がある。しかし、添加しすぎると材料が硬化し逆に加工性に悪影響をもたらす。また、再結晶温度を上げることから、０．１０〜０．８０％とした。 Nb is an element that fixes C and N and improves impact resistance and secondary workability, and has an effect of improving workability for battery case processing. However, if it is added too much, the material will be hardened and adversely affect the workability. Further, since the recrystallization temperature is raised, the content is made 0.10 to 0.80%.
ＴｉはＣ，Ｎを固定し、加工性および耐食性を向上させる元素である。しかし、添加しすぎると絞り加工における割れの原因となるＴｉ系介在物などの表面欠陥が存在することから、添加する場合は０．０５〜０．４０％とする。 Ti is an element that fixes C and N and improves workability and corrosion resistance. However, if too much is added, surface defects such as Ti-based inclusions that cause cracks in drawing work exist, so 0.05% to 0.40% when added.
Ａｌは脱酸や耐酸化性のために有効な元素であるが、過剰な添加は表面欠陥の原因となるため、添加する場合は０．０１〜０．５０％とした。 Al is an effective element for deoxidation and oxidation resistance, but excessive addition causes surface defects, so when added, the content was made 0.01 to 0.50%.
Ｂは、Ｎを固定し、耐食性や加工性を改善する作用をもつ合金成分であり、必要に応じて添加される。上記作用を発揮させるためには０．００５％以上添加することが望ましい。しかし、過剰に添加すると熟間加工性の低下や溶接性の低下を招くため、０．３％以下とした。 B is an alloy component that has the effect of fixing N and improving the corrosion resistance and workability, and is added as necessary. In order to exert the above action, it is desirable to add 0.005% or more. However, if added in excess, it causes a decrease in maturing workability and a decrease in weldability, so the content was made 0.3% or less.
以下の元素は請求項の中では記載していないが、不可避的に含まれるＰ，Ｓ以外に下記の元素を含有してもさしつかえない。 Although the following elements are not described in the claims, they may contain the following elements in addition to P and S which are inevitably included.
Ｖ、Ｚｒ：固溶Cを炭化物として析出させる効果による加工性向上、Ｚｒは鋼中の酸素を酸化物として捕えることによる加工性や靭性向上の面から有用な元素である。しかしながら、多量に添加すると製造性が低下するので、Ｖ、Ｚｒの適正含有量は０．０１〜０．３０％である。
これら以外にもＣａ、Ｍｇ、Ｃｏ、ＲＥＭなどは、溶製中に原料であるスクラップ中より含まれることもあるが、とりたてて多量に含まれる場合を除き、耐食性や加工性には影響ない。
V, Zr: Workability improvement by the effect of precipitating solute C as carbide, Zr is a useful element from the viewpoint of workability and toughness improvement by capturing oxygen in steel as an oxide. However, since the manufacturability decreases when added in a large amount, the appropriate content of V and Zr is 0.01 to 0.30%.
In addition to these, Ca, Mg, Co, REM, and the like may be contained in the scrap, which is a raw material, during melting, but do not affect the corrosion resistance and workability unless they are contained in large amounts.
表1の成分組成をもつステンレス鋼板を実験室的に真空溶解し、圧延、焼鈍により１．０ｍｍｔの冷延焼鈍板を作製した。表1中の鋼Ｎｏ．Ａ〜Ｊは化学成分値が本発明の範囲内にある本発明鋼である。それらのステンレス鋼に酸洗および熱処理を施し不動態皮膜を制御した。Ｃｒ濃度を上げるには再不動態化能の強３０％硝酸で酸洗し、不動態皮膜を厚くするためには大気中で４００℃の焼鈍を行なった。不動態皮膜の組成解析はＥＳＣＡにより行った。最表層の金属濃度よりＣｒ／（Ｆｅ＋Ｃｒ）を算出した。不動態皮膜の厚みはＥＳＣＡによる。ピークの半価値より算出した。 A stainless steel plate having the composition shown in Table 1 was melted in a laboratory vacuum, and a 1.0 mmt cold-rolled annealed plate was produced by rolling and annealing. Steel No. in Table 1 A to J are steels of the present invention whose chemical component values are within the scope of the present invention. These stainless steels were pickled and heat treated to control the passive film. In order to increase the Cr concentration, pickling with 30% nitric acid having strong repassivation ability was performed, and in order to increase the thickness of the passivation film, annealing was performed at 400 ° C. in the atmosphere. The composition analysis of the passive film was performed by ESCA. Cr / (Fe + Cr) was calculated from the metal concentration of the outermost layer. The thickness of the passive film depends on ESCA. Calculated from the half value of the peak.
これらの供試材において、Ｌｉ電池の電解液として用いられる１ＭのＬｉＣｌ０４／ＰＣ中で参照電極および対極にＬｉ板を用いて、ポテンショスタットによりＬｉ電極に対する分極曲線を測定した。測定は２０℃で実施し、自然電位より２０ｍＶ／ｍｉｎの走査速度で分極した。３．６ＶｖｓＬｉおよび４．５ＶｖｓＬｉの電位における電流の大小で各供試材の電解液に対する耐食性を評価した。表２に測定結果を示す。比較に普通鋼、ＣｕおよびＡｌの測定結果も示す。 In these test materials, a polarization curve with respect to the Li electrode was measured by a potentiostat using a Li plate as a reference electrode and a counter electrode in 1M LiCl0 4 / PC used as an electrolyte for a Li battery. Measurement was performed at 20 ° C., and polarization was performed at a scanning rate of 20 mV / min from the natural potential. The corrosion resistance of each sample material to the electrolyte was evaluated based on the magnitude of current at potentials of 3.6 V vs Li and 4.5 V vs Li. Table 2 shows the measurement results. The measurement results of ordinary steel, Cu and Al are also shown for comparison.
本発明鋼であるＡ〜Ｊ鋼は３．６ＶｖｓＬｉ時には溶解電流が検出されずに、４．５ＶｖｓＬｉ時に微小な溶解電流が観察されるのみであった。Ｌｉ電池の電極材、ケース材として使用されているＡｌ同等の耐食性を示した。一方、本発明よりＣｒの成分が外れるＥ鋼は発明鋼と比較すると高い電流値を示し、Ａｌよりも腐食電流が高かった。したがって、本発明成分および不動態皮膜のＣｒ比率を有さなければ電解液環境で耐食性を維持できないことがわかった。さらに本発明のＣ鋼を熱処理することにより不動態皮膜厚みを厚くしたＦ鋼は３．６ＶｖｓＬｉ時には腐食電流が検出されなかったが、４．５ＶｖｓＬｉ時にはＡｌより高い腐食電流が検出された。したがって、本電解液環境においては不動態皮膜厚みを本発明技術内に制御する必要があることがわかった。 In the steels A to J, which are the steels of the present invention, no melting current was detected at 3.6 V vs Li, and only a minute melting current was observed at 4.5 V vs Li. Corrosion resistance equivalent to Al used as an electrode material and a case material of a Li battery was shown. On the other hand, E steel from which the Cr component was removed from the present invention showed a higher current value than the inventive steel, and the corrosion current was higher than that of Al. Therefore, it was found that the corrosion resistance cannot be maintained in the electrolyte environment unless the Cr ratio of the component of the present invention and the passive film is provided. Furthermore, although the corrosion current was not detected at the time of 3.6VvsLi, F steel which thickened the passive film thickness by heat-treating C steel of the present invention detected the corrosion current higher than Al at 4.5VvsLi. Therefore, it was found that the passive film thickness needs to be controlled within the technique of the present invention in the present electrolytic solution environment.
本発明のステンレス鋼を電極材および電極ケースに用いることにより、自動車搭載用などに開発が進められている大容量バッテリーの安全性向上、軽量化、高性能化に寄与することが可能となった。本発明は自動車用以外にも設置型の大容量電池に適用可能で、さらにLi電池に限らず非水系の電解液を有する電池には全般的に適用可能である。 By using the stainless steel of the present invention for the electrode material and the electrode case, it has become possible to contribute to the improvement of safety, weight reduction, and high performance of a large-capacity battery being developed for use in automobiles. . The present invention can be applied not only to automobiles but also to installed large-capacity batteries, and not only to Li batteries but also to batteries having non-aqueous electrolytes in general.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008008597A JP2009167486A (en) | 2008-01-18 | 2008-01-18 | Ferritic stainless steel for battery component member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008008597A JP2009167486A (en) | 2008-01-18 | 2008-01-18 | Ferritic stainless steel for battery component member |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2009167486A true JP2009167486A (en) | 2009-07-30 |
Family
ID=40969002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008008597A Pending JP2009167486A (en) | 2008-01-18 | 2008-01-18 | Ferritic stainless steel for battery component member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2009167486A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140095071A (en) | 2011-10-30 | 2014-07-31 | 가부시키가이샤 니혼 마이크로닉스 | Repeatedly chargeable and dischargeable quantum battery |
| CN104094443A (en) * | 2012-05-22 | 2014-10-08 | 株式会社杰士汤浅国际 | Electricity storage element |
| JP2015086470A (en) * | 2013-09-26 | 2015-05-07 | 日新製鋼株式会社 | Stainless steel sheet having reduced elution amount in nonaqueous electrolyte, method for producing the same, and exterior member of nonaqueous electrolyte |
| JP6016987B1 (en) * | 2015-05-29 | 2016-10-26 | 日新製鋼株式会社 | Stainless steel foil for battery exterior and manufacturing method thereof |
| JP6016988B1 (en) * | 2015-05-29 | 2016-10-26 | 日新製鋼株式会社 | Stainless steel foil for battery exterior and manufacturing method thereof |
| WO2021005919A1 (en) | 2019-07-09 | 2021-01-14 | Ｊｆｅスチール株式会社 | Chromium-containing steel sheet for collectors of nonaqueous electrolyte secondary batteries and method for producing same |
| JP2021011620A (en) * | 2019-07-09 | 2021-02-04 | Ｊｆｅスチール株式会社 | Ferritic stainless steel sheet for collectors of sulfide-based solid-state batteries |
| JPWO2020004595A1 (en) * | 2018-06-27 | 2021-03-25 | 日鉄ケミカル＆マテリアル株式会社 | Secondary battery Stainless steel foil current collector for positive electrode and secondary battery |
| JP2022509863A (en) * | 2018-11-29 | 2022-01-24 | ポスコ | Ferritic stainless steel with improved corrosion resistance and its manufacturing method |
| WO2022131189A1 (en) | 2020-12-15 | 2022-06-23 | Ｊｆｅスチール株式会社 | Chromium-containing steel sheet for current collectors for nonaqueous electrolyte secondary batteries |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003257384A (en) * | 2002-02-28 | 2003-09-12 | Nisshin Steel Co Ltd | Ferritic stainless steel for button type lithium secondary battery case and battery case |
| JP2004149920A (en) * | 2002-10-07 | 2004-05-27 | Jfe Steel Kk | Stainless steel for separator of solid polymer fuel cell and its manufacturing method, and solid polymer fuel cell using that stainless steel |
| JP2005298939A (en) * | 2004-04-15 | 2005-10-27 | Jfe Steel Kk | Stainless steel sheet having superior corrosion resistance and electroconductivity |
-
2008
- 2008-01-18 JP JP2008008597A patent/JP2009167486A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003257384A (en) * | 2002-02-28 | 2003-09-12 | Nisshin Steel Co Ltd | Ferritic stainless steel for button type lithium secondary battery case and battery case |
| JP2004149920A (en) * | 2002-10-07 | 2004-05-27 | Jfe Steel Kk | Stainless steel for separator of solid polymer fuel cell and its manufacturing method, and solid polymer fuel cell using that stainless steel |
| JP2005298939A (en) * | 2004-04-15 | 2005-10-27 | Jfe Steel Kk | Stainless steel sheet having superior corrosion resistance and electroconductivity |
Non-Patent Citations (2)
| Title |
|---|
| JPN6012048852; Ｈｅｌｉ Ｗａｎｇ、Ｊｏｈｎ Ａ．Ｔｕｒｎｅｒ: 'Ｆｅｒｒｉｔｉｃ ｓｔａｉｎｌｅｓｓ ｓｔｅｅｌｓ ａｓ ｂｉｐｏｌａｒ ｐｌａｔｅ ｍａｔｅｒｉａｌ ｆｏｒ ｐｏｌｙｍｅｒ ｅｌｅｃｔｒｏｌｙｔｅ ｍｅｍｂｒａｎｅ ｆｕｅｌ ｃｅｌｌｓ' Ｊｏｕｒｎａｌ ｏｆ Ｐｏｗｅｒ Ｓｏｕｒｃｅｓ Ｖｏｌ．１２８ Ｎｏ．２, 20040405, Ｐａｇｅ．１９３-２００ * |
| JPN6012048855; Ｚｈｅｎｇｕｏ Ｙａｎｇ、他５名: 'Ｓｔｒｕｃｔｕｒｅ ａｎｄ Ｃｏｎｄｕｃｔｉｖｉｔｙ ｏｆ Ｔｈｅｒｍａｌｌｙ Ｇｒｏｗｎ Ｓｃａｌｅｓ ｏｎ Ｆｅｒｒｉｔｉｃ Ｆｅ-Ｃｒ-Ｍｎ Ｓｔｅｅｌ ｆｏｒ ＳＯＦＣ Ｉｎｔｅｒｃｏｎｎｅｃ' Ｊｏｕｒｎａｌ ｏｆ Ｔｈｅ Ｅｌｅｃｔｒｏｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ Ｖｏｌ．１５１ Ｎｏ．１１, 2004, Ｐａｇｅ．Ａ１８２５-Ａ１８３１ * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9859596B2 (en) | 2011-10-30 | 2018-01-02 | Kabushiki Kaisha Nihon Micronics | Repeatedly chargeable and dischargeable quantum battery |
| KR20140095071A (en) | 2011-10-30 | 2014-07-31 | 가부시키가이샤 니혼 마이크로닉스 | Repeatedly chargeable and dischargeable quantum battery |
| CN104094443A (en) * | 2012-05-22 | 2014-10-08 | 株式会社杰士汤浅国际 | Electricity storage element |
| JP2015086470A (en) * | 2013-09-26 | 2015-05-07 | 日新製鋼株式会社 | Stainless steel sheet having reduced elution amount in nonaqueous electrolyte, method for producing the same, and exterior member of nonaqueous electrolyte |
| US10903461B2 (en) | 2015-05-29 | 2021-01-26 | Nisshin Steel Co., Ltd. | Battery armoring stainless steel foil, and method of producing same |
| WO2016194660A1 (en) * | 2015-05-29 | 2016-12-08 | 日新製鋼株式会社 | Stainless steel foil for battery outer packaging |
| JP2016225134A (en) * | 2015-05-29 | 2016-12-28 | 日新製鋼株式会社 | Stainless foil for battery outer packaging and manufacturing method of same |
| JP2016225133A (en) * | 2015-05-29 | 2016-12-28 | 日新製鋼株式会社 | Stainless foil for battery outer packaging and manufacturing method of same |
| JP6016988B1 (en) * | 2015-05-29 | 2016-10-26 | 日新製鋼株式会社 | Stainless steel foil for battery exterior and manufacturing method thereof |
| US10087498B2 (en) | 2015-05-29 | 2018-10-02 | Nisshin Steel Co., Ltd. | Battery armoring stainless steel foil, and method of producing same |
| JP6016987B1 (en) * | 2015-05-29 | 2016-10-26 | 日新製鋼株式会社 | Stainless steel foil for battery exterior and manufacturing method thereof |
| WO2016194661A1 (en) * | 2015-05-29 | 2016-12-08 | 日新製鋼株式会社 | Stainless steel foil for battery outer packaging |
| JP7148608B2 (en) | 2018-06-27 | 2022-10-05 | 日鉄ケミカル＆マテリアル株式会社 | Stainless foil current collector for secondary battery positive electrode and secondary battery |
| JPWO2020004595A1 (en) * | 2018-06-27 | 2021-03-25 | 日鉄ケミカル＆マテリアル株式会社 | Secondary battery Stainless steel foil current collector for positive electrode and secondary battery |
| JP2022509863A (en) * | 2018-11-29 | 2022-01-24 | ポスコ | Ferritic stainless steel with improved corrosion resistance and its manufacturing method |
| JP7427669B2 (en) | 2018-11-29 | 2024-02-05 | ポスコ カンパニー リミテッド | Ferritic stainless steel with improved corrosion resistance and its manufacturing method |
| KR20220008900A (en) * | 2019-07-09 | 2022-01-21 | 제이에프이 스틸 가부시키가이샤 | Ferritic stainless steel sheet for current collector of sulfide-based solid battery |
| CN113994020A (en) * | 2019-07-09 | 2022-01-28 | 杰富意钢铁株式会社 | Ferritic stainless steel sheet for current collector of sulfide-based solid battery |
| JP7014754B2 (en) | 2019-07-09 | 2022-02-01 | Ｊｆｅスチール株式会社 | Ferritic stainless steel sheet for collectors of sulfide-based solid-state batteries |
| KR20220017484A (en) | 2019-07-09 | 2022-02-11 | 제이에프이 스틸 가부시키가이샤 | Chromium-containing steel sheet for current collector of nonaqueous electrolyte secondary battery and manufacturing method thereof |
| EP3998367A4 (en) * | 2019-07-09 | 2022-09-21 | JFE Steel Corporation | Ferritic stainless steel sheet for collectors of sulfide-based solid-state batteries |
| JP2021011620A (en) * | 2019-07-09 | 2021-02-04 | Ｊｆｅスチール株式会社 | Ferritic stainless steel sheet for collectors of sulfide-based solid-state batteries |
| WO2021005919A1 (en) | 2019-07-09 | 2021-01-14 | Ｊｆｅスチール株式会社 | Chromium-containing steel sheet for collectors of nonaqueous electrolyte secondary batteries and method for producing same |
| KR102638365B1 (en) * | 2019-07-09 | 2024-02-19 | 제이에프이 스틸 가부시키가이샤 | Ferrite-based stainless steel sheet for current collectors in sulfide-based solid-state batteries |
| WO2022131189A1 (en) | 2020-12-15 | 2022-06-23 | Ｊｆｅスチール株式会社 | Chromium-containing steel sheet for current collectors for nonaqueous electrolyte secondary batteries |
| KR20230098873A (en) | 2020-12-15 | 2023-07-04 | 제이에프이 스틸 가부시키가이샤 | Chromium-containing steel sheet for current collector of non-aqueous electrolyte secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2009167486A (en) | Ferritic stainless steel for battery component member | |
| TWI437104B (en) | Ferritic stainless steel having excellent corrosion resistance and conductivity and method of the same, separator of proton-exchange membrane fuel cell and proton-exchange membrane fuel cell | |
| JP6726735B2 (en) | Stainless steel for fuel cell separator and method of manufacturing the same | |
| JP6315158B1 (en) | Stainless steel sheet and method for producing the same, separator for polymer electrolyte fuel cell, polymer electrolyte fuel cell, and polymer electrolyte fuel cell | |
| JP5334485B2 (en) | Current collector and negative electrode material for lithium ion secondary battery | |
| JP5218612B2 (en) | Stainless steel for fuel cell separator | |
| JP5971446B1 (en) | Ferritic stainless steel material, polymer electrolyte fuel cell separator and polymer electrolyte fuel cell using the same | |
| JP2000328200A (en) | Austenitic stainless steel for conductive electric parts and fuel battery | |
| WO2013018322A1 (en) | Stainless steel for fuel cell separator | |
| JP4437036B2 (en) | Case material for storage cells | |
| KR102638365B1 (en) | Ferrite-based stainless steel sheet for current collectors in sulfide-based solid-state batteries | |
| JP2010106305A (en) | Stainless steel for cell composing member and method for producing the same | |
| JP3269479B2 (en) | Ferritic stainless steel for polymer electrolyte fuel cell separator | |
| WO2016129598A1 (en) | Ferritic stainless steel material, separator, solid polymer fuel cell, and method for producing separator | |
| JP2000309854A (en) | Austenitic stainless steel for current-carrying electric parts, and fuel cell | |
| JP2014191941A (en) | Current collector for aqueous solution-based lithium ion battery | |
| CN112262225B (en) | Stainless steel foil collector for secondary battery positive electrode | |
| JP2020506499A (en) | Stainless steel for polymer fuel cell separator having excellent contact resistance and method for producing the same | |
| JP2020111806A (en) | Stainless steel sheet and method for producing the same, separator for fuel battery, fuel battery cell, and fuel battery stack | |
| JP3433435B2 (en) | Stainless steel with excellent resistance to molten carbonate corrosion | |
| JP7305890B2 (en) | Manufacturing method of stainless steel for polymer fuel cell separator | |
| JP7257793B2 (en) | Stainless steel plate, fuel cell separator, fuel cell, and fuel cell stack | |
| KR20240028470A (en) | Stainless steel plates, separators for fuel cells, fuel cell cells, and fuel cell stacks |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110118 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120905 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120925 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121122 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130305 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20130709 |