JP2015074798A - Ferritic stainless steel for lithium ion secondary battery electrolyte storage container and lithium ion secondary battery electrolyte storage container using the same - Google Patents
Ferritic stainless steel for lithium ion secondary battery electrolyte storage container and lithium ion secondary battery electrolyte storage container using the same Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 50
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- 238000003860 storage Methods 0.000 title claims abstract description 34
- 230000007797 corrosion Effects 0.000 claims abstract description 32
- 238000005260 corrosion Methods 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000005554 pickling Methods 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 12
- 230000003628 erosive effect Effects 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 15
- 239000010959 steel Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- 230000001965 increasing effect Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 4
- 229940021013 electrolyte solution Drugs 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002436 steel type Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 101150004907 litaf gene Proteins 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Abstract
Description
本発明は、リチウムイオン二次電池電解液保管容器向けの金属材料に関する。電解液の取扱いにおいて、液こぼれが起こった場合でも、十分な耐食性を有するフェライト系ステンレス鋼を提供するものである。 The present invention relates to a metal material for a lithium ion secondary battery electrolyte storage container. The present invention provides a ferritic stainless steel having sufficient corrosion resistance even when liquid spillage occurs during the handling of an electrolytic solution.
リチウムイオン二次電池は、エネルギー密度が高く、メモリー効果も小さいことから、携帯電話やハイブリッドカーを含めた電気自動車に用いられている。リチウムイオン二次電池の電解液は、エチレンカーボネート（ＥＣ）やジエチルカーボネート（ＤＥＣ）などの有機溶媒に、電解質として６弗化リン酸リチウム（ＬｉＰＦ６）を加えたものを主成分とする。なお６弗化リン酸リチウムは、空気中の酸素や水蒸気と反応し、弗酸を生じるため、電解液が空気と接触すると、腐食性が増すことが知られている。 Lithium ion secondary batteries are used for electric vehicles including mobile phones and hybrid cars because of their high energy density and low memory effect. The electrolyte solution of the lithium ion secondary battery is mainly composed of an organic solvent such as ethylene carbonate (EC) or diethyl carbonate (DEC) added with lithium hexafluorophosphate (LiPF 6 ) as an electrolyte. It is known that lithium hexafluorophosphate reacts with oxygen and water vapor in the air to generate hydrofluoric acid, so that the corrosiveness increases when the electrolytic solution comes into contact with air.
電解液の保管や輸送に用いる容器（以下、「電解液保管容器」と称する。）として、かつては樹脂容器が用いられることもあったが、現在では、密閉性、耐久性に優れるステンレス鋼製の容器が主流となっている。 Resin containers were once used as containers for storing and transporting electrolytes (hereinafter referred to as “electrolyte storage containers”), but now they are made of stainless steel with excellent sealing and durability. The container has become mainstream.
容器の素材としては、ＳＵＳ３０４、ＳＵＳ３１６などのオーステナイト系ステンレス鋼が一般的に用いられている。オーステナイト系ステンレス鋼は耐食性が高いため、電解液の取扱いにおいて液がこぼれて空気と接触し、電解液の腐食性が増した場合であっても容器の使用に支障を生じるような腐食は起こりにくい。 As the material of the container, austenitic stainless steel such as SUS304 and SUS316 is generally used. Since austenitic stainless steel has high corrosion resistance, even when the electrolyte spills and comes into contact with air during handling of the electrolyte, corrosion that hinders the use of the container is unlikely to occur even if the corrosion of the electrolyte increases. .
一方、近年のリチウムイオン二次電池の生産量増加とともに、電解液保管容器のコストダウンの要求が高くなってきた。したがって、容器の大型化や形状の最適化、製造方法の改善が行われると同時に、素材の見直しが検討されている。 On the other hand, with the recent increase in production of lithium ion secondary batteries, the demand for cost reduction of electrolyte storage containers has increased. Therefore, the review of the material is being considered at the same time as the container is enlarged, the shape is optimized, and the manufacturing method is improved.
オーステナイト系ステンレス鋼よりも安価な鋼種として、フェライト系ステンレス鋼がある。しかし、一般的にフェライト系ステンレス鋼はオーステナイト系ステンレス鋼に比較して耐食性が劣ると考えられており、これまで使用されていなかった。そのため、空気と接触して腐食性が増した電解液に対する耐食性に優れるフェライト系ステンレス鋼が望まれていた。 Ferritic stainless steel is a cheaper steel type than austenitic stainless steel. However, in general, ferritic stainless steel is considered to be inferior in corrosion resistance compared to austenitic stainless steel, and has not been used so far. Therefore, a ferritic stainless steel that is excellent in corrosion resistance against an electrolytic solution that has increased corrosivity upon contact with air has been desired.
リチウムイオン二次電池用途のフェライト系ステンレス鋼として、特許文献１に開示される技術が知られている。これは、リチウムイオン二次電池ケースとしてフェライト系ステンレス鋼を用いる技術であり、内面にポリプロピレンフィルムを付着させることを特徴としている。リチウムイオン二次電池ケースでは電解液が漏洩した際の耐食性までは要求されていないため、このような技術で十分であった。しかし電解液保管容器の場合は、電解液がこぼれることも想定しなければならず、特許文献１に開示される技術では十分な耐食性が得られなかった。
The technique disclosed in
なお、耐食性の他に、電解液容器の品質向上のための要素として、内面の清浄性がある。金属粉のようなパーティクルが電解液に混入すると、電池の性能を低下させる場合があり、対策として容器内面に酸洗、電解研磨を施している。従って、フェライト系ステンレス鋼を用いた電解液容器の品質向上のため、フェライト系ステンレス鋼に適した酸洗、電解研磨条件を把握することが好ましい。 In addition to corrosion resistance, there is cleanliness of the inner surface as an element for improving the quality of the electrolyte container. If particles such as metal powder are mixed in the electrolytic solution, the performance of the battery may be deteriorated. As a countermeasure, pickling and electrolytic polishing are performed on the inner surface of the container. Therefore, in order to improve the quality of the electrolytic solution container using ferritic stainless steel, it is preferable to grasp the pickling and electropolishing conditions suitable for the ferritic stainless steel.
上記状況を踏まえ、本発明は、リチウムイオン二次電池の電解液保管容器のための耐食性に優れたフェライト系ステンレス鋼を提供することを目的とする。 In view of the above situation, an object of the present invention is to provide a ferritic stainless steel having excellent corrosion resistance for an electrolyte storage container of a lithium ion secondary battery.
さらに、得られたフェライト系ステンレス鋼から製造されたリチウムイオン二次電池の電解液保管容器の耐食性向上のための、最適の酸洗もしくは電解研磨条件を検討し、当該最適な条件で施術されたステンレス鋼製リチウムイオン二次電池電解液保管容器もまた提供する。 In addition, we investigated the optimum pickling or electropolishing conditions for improving the corrosion resistance of the electrolyte storage container of the lithium ion secondary battery manufactured from the ferritic stainless steel obtained, and the treatment was performed under the optimum conditions. A stainless steel lithium ion secondary battery electrolyte storage container is also provided.
上記目的を達成するために、本発明者らは鋭意検討の結果、特定の構成を有するフェライト系ステンレス鋼が、リチウムイオン二次電池の電解液で使用される６弗化リン酸リチウムを含む溶液に対して著しい耐食性を示すことを見出した。 In order to achieve the above object, as a result of intensive studies, the present inventors have determined that a ferritic stainless steel having a specific configuration contains a solution containing lithium hexafluorophosphate used in an electrolyte of a lithium ion secondary battery. It has been found that it exhibits remarkable corrosion resistance.
つまり、本発明は、電池の電解質で使用されるＣ：０．０２質量％以下、Ｓｉ：０．８０質量％以下、Ｍｎ：０．８０質量％以下、Ｐ：０．０４質量％以下、Ｓ：０．０１０質量％以下、Ｃｒ：１６．０〜３５．０質量％、Ｎ：０．０２５質量％以下、Ａｌ：０．００３〜０．２０質量％、Ｎｂ：０．８０質量％、Ｔｉ：０．６０質量％以下を含有し、残部がＦｅおよび不可避的不純物からなり、さらに（Ｔｉ＋Ｎｂ）≧７×（Ｃ＋Ｎ）であるリチウムイオン二次電池電解液保管容器用フェライト系ステンレス鋼を提供することを目的とする。 That is, the present invention uses C: 0.02 mass% or less, Si: 0.80 mass% or less, Mn: 0.80 mass% or less, P: 0.04 mass% or less, S used in the battery electrolyte. : 0.010 mass% or less, Cr: 16.0 to 35.0 mass%, N: 0.025 mass% or less, Al: 0.003 to 0.20 mass%, Nb: 0.80 mass%, Ti : Ferrite stainless steel for lithium ion secondary battery electrolyte storage container containing 0.60% by mass or less, the balance being Fe and inevitable impurities, and further (Ti + Nb) ≧ 7 × (C + N) For the purpose.
さらに、上記フェライト系ステンレス鋼製リチウム二次電池電解液保管容器、さらに該容器の品質向上のための最適な酸洗または電解研磨条件を提供し、係る条件下で処理を施したリチウム二次電池電解液保管容器も提供する。 Furthermore, the lithium secondary battery electrolyte storage container made of the above ferritic stainless steel, further providing the optimum pickling or electropolishing conditions for improving the quality of the container, and the lithium secondary battery treated under such conditions An electrolyte storage container is also provided.
本発明により、空気と接触して腐食性が増したリチウムイオン二次電池電解液に対する耐食性が極めて良好なフェライト系ステンレス鋼が得られる。特に、リチウムイオン二次電池電解液に対する耐食性試験の結果が極めて良好であり、該鋼板を用いて製造された電解液保管容器は長期間使用することができる。 According to the present invention, a ferritic stainless steel having extremely good corrosion resistance against a lithium ion secondary battery electrolyte that is in contact with air and has increased corrosivity can be obtained. In particular, the result of the corrosion resistance test for the lithium ion secondary battery electrolyte is extremely good, and the electrolyte storage container manufactured using the steel sheet can be used for a long time.
本発明のフェライト系ステンレス鋼を構成する各合金元素について範囲選定理由について説明する。 The reason for selecting the range for each alloy element constituting the ferritic stainless steel of the present invention will be described.
Ｃ：０．０２質量％以下、Ｎ：０．０２５質量％以下
Ｃ、Ｎはステンレス鋼中に不可避的に含まれる元素である。Ｃ含有量およびＮ含有量を低減すると、炭化物、窒化物の生成が少なくなり、溶接性および溶接部の耐食性が向上する。しかし、低減のためには精錬時間が長くなり、ステンレス鋼製造のコスト上昇を招くため、Ｃは０．０２０質量％まで、Ｎは０．０２５質量％までの含有を許容することにした。
C: 0.02 mass% or less, N: 0.025 mass% or less C and N are elements inevitably contained in stainless steel. When the C content and the N content are reduced, the formation of carbides and nitrides is reduced, and the weldability and the corrosion resistance of the welded portion are improved. However, since the refining time becomes longer for the reduction and the cost of the stainless steel production increases, it was decided to allow the content of C up to 0.020 mass% and N up to 0.025 mass%.
Ｓｉ：０．８０質量％以下
Ｓｉはステンレス鋼の脱酸剤として添加される。しかし、過剰のＳｉ含有はフェライト相を硬質化させ、加工性や靭性を劣化させる要因となることから、本発明においては上限を０．８０質量％とする。
Si: 0.80 mass% or less Si is added as a deoxidizer for stainless steel. However, excessive Si content hardens the ferrite phase and causes deterioration of workability and toughness. Therefore, in the present invention, the upper limit is set to 0.80% by mass.
Ｍｎ：０．８０質量％以下
Ｍｎはステンレス鋼に不純物として含まれているＳと結合し、化学的に不安定な硫化物であるＭｎＳを形成して耐食性を低下させる。したがってＭｎ含有量は低いほど好ましく、本発明においては、０．８０質量％を上限とする。
Mn: 0.80% by mass or less Mn combines with S contained as an impurity in stainless steel to form MnS, which is a chemically unstable sulfide, and lowers the corrosion resistance. Therefore, the lower the Mn content, the better. In the present invention, the upper limit is 0.80% by mass.
Ｐ：０．０４質量％以下
Ｐは、母材およびろう付け部の靭性を損なうので低い方が望ましい。ただし、含Ｃｒ鋼の溶製において精錬による脱Ｐは困難であることから、Ｐ含有量を極低化するには原料の厳選などに過剰なコスト増を伴う。したがって本発明では一般的なフェライト系ステンレス鋼と同様に、０.０４質量％までのＰ含有を許容する。
P: 0.04% by mass or less P is preferably as low as possible because it impairs the toughness of the base material and the brazed part. However, since it is difficult to remove P by refining in the production of Cr-containing steel, excessively increasing the cost for selecting raw materials or the like is accompanied by extremely low P content. Therefore, in the present invention, the P content up to 0.04% by mass is allowed as in the general ferritic stainless steel.
Ｓ：０．０１０質量％以下
Ｓは、ＭｎＳを形成し、酸洗や電解研磨によってＭｎＳ周辺にピットが生じやすくなる。したがって、Ｓ含有量は低いほど好ましく、本発明では０.０１０質量％以下に規定される。
S: 0.010% by mass or less S forms MnS, and pits are easily generated around MnS by pickling or electrolytic polishing. Therefore, the lower the S content, the better. In the present invention, the S content is defined as 0.010% by mass or less.
Ｃｒ：１６．０〜３５．０質量％
Ｃｒは、不動態皮膜の主要構成元素であり、耐食性の向上をもたらす。電解液が空気と接触しない場合であれば、特許文献１に開示されているとおり、１０質量％以上含有すれば良い。しかし、作業時の液こぼれ等によって大気に触れ、腐食性が増した場合には、Ｃｒを１６．０質量％以上含有しなければ、耐食性を示すことができない。一方、Ｃｒ含有量が多くなるとＣ、Ｎの低減が難しくなり、機械的性質や靭性を損ね、かつコストを増大させる要因となる。したがって本発明ではＣｒ含有量を１６．０〜３５質量％とする。
Cr: 16.0-35.0 mass%
Cr is a main constituent element of the passive film, and improves corrosion resistance. If the electrolytic solution is not in contact with air, it may be contained at 10% by mass or more as disclosed in
Ｍｏ：２．５質量％以下
Ｍｏは耐食性を高めるのに有効な元素であり、必要に応じて添加される。過度の添加は加工性を損ね、かつコストを増大させる要因となる。したがって、添加する場合、本発明ではＭｏ含有量を２．５質量％以下とする。なお、所望の効果を期待するためには、好ましくはＭｏ含有量を０．０２質量％以上とする。
Mo: 2.5 mass% or less Mo is an element effective for enhancing corrosion resistance, and is added as necessary. Excessive addition impairs processability and increases the cost. Therefore, when adding, in this invention, Mo content shall be 2.5 mass% or less. In addition, in order to expect a desired effect, Preferably Mo content shall be 0.02 mass% or more.
Ｎｉ：２．０質量％以下
Ｎｉは耐食性を高めるのに有効な元素であり、必要に応じて添加される。オーステナイト形成元素であり、過度に添加すると、フェライト単相組織を維持できなくなる。したがって、添加する場合、本発明ではＮｉ含有量を２．０質量％以下とする。なお、所望の効果を期待するためには、好ましくはＮｉ含有量を０．０２質量％以上とする。
Ni: 2.0% by mass or less Ni is an element effective for enhancing corrosion resistance, and is added as necessary. It is an austenite forming element, and if it is added excessively, the ferrite single phase structure cannot be maintained. Therefore, when it adds, in this invention, Ni content shall be 2.0 mass% or less. In addition, in order to expect a desired effect, Preferably Ni content shall be 0.02 mass% or more.
Ｃｕ：２．０質量％以下
Ｃｕは耐食性を高めるのに有効な元素であり、必要に応じて添加される。オーステナイト形成元素であり、過度に添加すると、フェライト単相組織を維持できなくなる。したがって、添加する場合、本発明ではＣｕ含有量を２．０質量％以下とする。なお、所望の効果を期待するために、好ましくはＣｕ含有量を０．０２質量％以上とする。
Cu: 2.0% by mass or less Cu is an element effective for enhancing corrosion resistance, and is added as necessary. It is an austenite forming element, and if it is added excessively, the ferrite single phase structure cannot be maintained. Therefore, when adding, Cu content shall be 2.0 mass% or less in this invention. In addition, in order to expect a desired effect, Preferably Cu content shall be 0.02 mass% or more.
Ａｌ：０．００３〜０．２０質量％
Ａｌは電解液に対する耐食性を高めるために有効な成分である。Ａｌが電解液中の６弗化リン酸リチウムと反応して安定な弗化物を形成し、Ｃｒを主体とする不動態皮膜とともに、耐食性を高めていると考えられる。その効果を発現するためには、０．００３質量％以上の添加が必要である。しかし過剰のＡｌ含有はフェライト相を硬質化させ、加工性や靭性を劣化させる要因となることから、本発明においてはＡｌ量の上限は０．２０質量％とする。
Al: 0.003 to 0.20 mass%
Al is an effective component for enhancing the corrosion resistance against the electrolytic solution. It is considered that Al reacts with lithium hexafluorophosphate in the electrolytic solution to form a stable fluoride and, together with a passive film mainly composed of Cr, enhances the corrosion resistance. In order to exhibit the effect, addition of 0.003% by mass or more is necessary. However, excessive Al content hardens the ferrite phase and causes deterioration of workability and toughness. Therefore, in the present invention, the upper limit of Al content is 0.20 mass%.
Ｎｂ：０．８０質量％以下
Ｎｂ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、過剰のＮｂ含有は、ステンレス鋼が硬質化し、加工性を損なうことから、本発明ではＮｂ量の上限を０．８０質量％とする。
Nb: 0.80% by mass or less Nb is an element that fixes C and N and improves workability and corrosion resistance. However, excessive Nb content hardens the stainless steel and impairs workability. Therefore, in the present invention, the upper limit of the Nb content is set to 0.80% by mass.
Ｔｉ：０．６０質量％以下
ＴｉはＮｂと同様に、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、過剰のＮｂ含有は、ステンレス鋼が硬質化し、加工性を損なうことから、本発明ではＴｉ量の上限を０．６０質量％とする。
Ti: 0.60% by mass or less Ti, like Nb, is an element that fixes C and N and improves workability and corrosion resistance. However, excessive Nb content hardens the stainless steel and impairs workability. Therefore, in the present invention, the upper limit of Ti content is set to 0.60% by mass.
（Ｔｉ＋Ｎｂ）≧７×（Ｃ＋Ｎ）
ＴｉおよびＮｂはＣ、Ｎを固定する目的で添加するものであるから、Ｃ、Ｎ量に応じた適量を添加する必要がある。本発明では、ＴｉとＮｂをあわせて、７×（Ｃ＋Ｎ）以上の添加を必要とする。
(Ti + Nb) ≧ 7 × (C + N)
Since Ti and Nb are added for the purpose of fixing C and N, it is necessary to add appropriate amounts according to the amounts of C and N. In the present invention, it is necessary to add 7 × (C + N) or more in combination of Ti and Nb.
以下に耐食性試験条件の選定理由を示す。
試験片形状
フェライト系ステンレス鋼は、乾湿繰り返し環境において、隙間腐食が進行しやすいことが知られている。したがって本発明においては、１５ｍｍ×１５ｍｍ×板厚１ｍｍの小片および４０ｍｍ×４０ｍｍ×板厚１ｍｍの大片をスポット溶接し、隙間を有する試験片を用いることとする。
The reasons for selecting the corrosion resistance test conditions are shown below.
It is known that the test piece-shaped ferritic stainless steel easily undergoes crevice corrosion in a wet and dry repeated environment. Accordingly, in the present invention, a small piece of 15 mm × 15 mm ×
電解液組成
リチウムイオン二次電池用の電解液としては種々の組成のものが開発されている。とはいえ、電解液の腐食性は、電解液が空気と触れ、６弗化リン酸リチウムと酸素あるいは水蒸気が反応して弗酸を形成することで生じるものであることから、本発明では、６弗化リン酸リチウムの濃度のみを規定し、その濃度を１ｍｏｌ／リットルとする。そのような電解液１００マイクロリットルを試験片の隙間部に滴下する。
Electrolyte Compositions Various compositions have been developed as electrolyte solutions for lithium ion secondary batteries. Nonetheless, the corrosiveness of the electrolytic solution is caused by the fact that the electrolytic solution comes into contact with air and lithium hexafluorophosphate reacts with oxygen or water vapor to form hydrofluoric acid. Only the concentration of lithium hexafluorophosphate is defined, and the concentration is 1 mol / liter. 100 microliters of such electrolyte is dropped into the gap between the test pieces.
乾湿繰り返し条件
上述の通り、腐食性は電解液が空気と触れることで生じることから、試験は大気中で行う必要がある。また、乾燥と湿潤を繰り返すと、乾燥から湿潤および湿潤から乾燥に移行する際に、電解液中に生じた弗酸の濃度が高くなり、腐食性が増すことから、試験は乾湿を繰り返す方法とした。夏場の気温を想定し、試験温度は５０℃とし、湿度は、種々検討した結果、最も腐食度が高かった相対湿度８５％とした。以上より、乾湿繰り返し条件は、５０℃、相対湿度８５％で３時間、５０℃、相対湿度３０％で１時間保持する過程を１サイクルとし、１００サイクル繰り返すこととする。
Repeated wet and dry conditions As described above, corrosiveness is caused by contact of the electrolyte with air, so the test must be performed in the atmosphere. In addition, when drying and wetting are repeated, the concentration of hydrofluoric acid generated in the electrolyte increases when shifting from drying to wetting and from moisture to drying. did. Assuming the summer temperature, the test temperature was set to 50 ° C., and the humidity was set to 85% relative humidity with the highest degree of corrosion as a result of various studies. From the above, the dry and wet conditions are 50 cycles at 50 ° C. and 85% relative humidity for 3 hours, 1 hour at 50 ° C. and 30% relative humidity for 1 cycle, and 100 cycles.
本発明のリチウムイオン二次電池電解液保管容器は、鋼板表面に存在するパーティクルを除去するために、その内面を酸洗浄もしくは電解研磨することが好ましい。
酸洗は、不動態皮膜を破壊した上で、Ｈ＋イオンの還元作用によってステンレス鋼を溶解させることによって行うものである。
In the lithium ion secondary battery electrolyte storage container of the present invention, the inner surface thereof is preferably acid-washed or electropolished in order to remove particles present on the surface of the steel sheet.
Pickling is performed by breaking the passive film and dissolving stainless steel by the reducing action of H + ions.
弗酸：０．５質量％以上、硝酸：５質量％以上
硝酸はＨ＋の供給源として、５質量％以上添加する必要がある。ただし、硝酸には不動態を破壊する作用がないため、硝酸を用いる場合は合わせて０．５質量％以上の弗酸を用いる必要がある。なお、弗酸を過剰に添加するとＦｅイオンと反応してＦｅＦ３として沈殿し、むしろ効果が低くなることがあるため弗酸濃度は５質量％以下であることが好ましい。硝酸は過剰に添加しても添加量に見合う効果の上昇は見込めず、コストの上昇を招くのみであるため、硝酸は１５質量％以下であることが好ましい。
Hydrofluoric acid: 0.5% by mass or more, Nitric acid: 5% by mass or more Nitric acid needs to be added by 5% by mass or more as a H + supply source. However, since nitric acid does not have an effect of destroying the passive state, when nitric acid is used, it is necessary to use 0.5% by mass or more of hydrofluoric acid. In addition, when hydrofluoric acid is added excessively, it reacts with Fe ions and precipitates as FeF 3 , and the effect is rather lowered. Therefore, the hydrofluoric acid concentration is preferably 5% by mass or less. Even if nitric acid is added excessively, an increase in effect commensurate with the amount of addition cannot be expected, and only an increase in cost is caused. Therefore, nitric acid is preferably 15% by mass or less.
塩酸：５質量％以上
塩酸はＨ＋イオンの供給源であり、さらにＣｌ−イオンによる不動態皮膜の破壊作用があることから、単独添加で５質量％以上添加すれば良い。なお、塩酸は過剰に添加しても添加量に見合う効果の上昇は見込めず、コストの上昇を招くのみであるため、塩酸濃度は１５質量％以下であることが好ましい。
Hydrochloric acid: 5% by mass or more Hydrochloric acid is a supply source of H + ions, and further has a destructive action on the passive film by Cl − ions, so it may be added alone by 5% by mass or more. In addition, even if hydrochloric acid is added excessively, an increase in effect commensurate with the amount added cannot be expected, and only an increase in cost is caused. Therefore, the hydrochloric acid concentration is preferably 15% by mass or less.
硫酸：１０質量％以上
硫酸はＨ＋イオンの供給源であり、不動態皮膜を破壊する作用はあるが、塩酸に比べるとその作用は小さいことから、１０質量％以上が必要である。なお、硫酸は過剰に添加しても添加量に見合う効果の上昇は見込めず、コストの上昇を招くのみであるため、硫酸濃度は２５質量％以下であることが好ましい。
Sulfuric acid: 10% by mass or more Sulfuric acid is a source of H + ions and has an effect of destroying the passive film, but its effect is small compared with hydrochloric acid, and thus 10% by mass or more is necessary. In addition, even if it adds sulfuric acid excessively, since the raise of the effect corresponding to the addition amount cannot be anticipated, and it causes only a raise of cost, it is preferable that a sulfuric acid concentration is 25 mass% or less.
上述した組成の酸洗液を電解液保管容器の内部に注入、あるいは酸洗液を満たした槽に、電解液保管容器を浸漬し、１分以上保持することにより、ステンレス鋼表面が溶解し、それに伴って表面の付着物が除去される。温度は常温でかまわないが、必要に応じて８０℃まで加温しても良い。
また、酸洗浄に要する時間は、酸洗液の酸の濃度や温度に依存するが所望の表面粗さが得られる時間であれば特に制限されない。しかし、通常は、１〜１０分、好ましくは１〜５分である。
By injecting the pickling solution having the above-described composition into the inside of the electrolytic solution storage container, or immersing the electrolytic solution storage container in a tank filled with the pickling solution and holding it for 1 minute or more, the stainless steel surface is dissolved, Along with this, surface deposits are removed. The temperature may be room temperature, but may be heated to 80 ° C. if necessary.
Further, the time required for the acid cleaning depends on the acid concentration and temperature of the pickling solution, but is not particularly limited as long as a desired surface roughness can be obtained. However, it is usually 1 to 10 minutes, preferably 1 to 5 minutes.
電解研磨は、電流を流すことでステンレス鋼を電気化学的に溶解させる方法である。特にリン酸を用いると、ステンレス鋼の表面に電気抵抗の高い液膜が形成され、平滑な表面性状を得ることができるものである。
具体的に、下記の溶液を満たした槽に電極を入れ、電解液保管容器を浸漬し、電流密度２０〜５００ｍＡ／ｃｍ２で、１分以上保持することにより、ステンレス鋼表面が溶解し、それに伴って表面の付着物が除去される。槽の溶液の温度は常温でかまわないが、必要に応じて８０℃まで加温しても良い。
また、電解研磨に要する時間は、電流密度や電解研磨に使用する溶液の酸の濃度に依存するが、所望の表面粗さが得られる時間であれば特に制限されない。しかし、通常１〜１０分、好ましくは１〜５分である。
Electropolishing is a method in which stainless steel is dissolved electrochemically by passing an electric current. In particular, when phosphoric acid is used, a liquid film having high electrical resistance is formed on the surface of stainless steel, and smooth surface properties can be obtained.
Specifically, an electrode is put in a tank filled with the following solution, an electrolytic solution storage container is immersed, and held at a current density of 20 to 500 mA / cm 2 for 1 minute or more, thereby dissolving the stainless steel surface. At the same time, surface deposits are removed. The temperature of the solution in the tank may be room temperature, but may be heated up to 80 ° C. if necessary.
The time required for electropolishing depends on the current density and the acid concentration of the solution used for electropolishing, but is not particularly limited as long as the desired surface roughness can be obtained. However, it is usually 1 to 10 minutes, preferably 1 to 5 minutes.
リン酸：１０質量％以上
リン酸水溶液中で電解研磨を行う場合、リン酸濃度は１０質量％以上にする必要がある。これよりも低い濃度の場合は、ステンレス鋼表面に電気抵抗の高い液膜を形成することができず、平滑な表面性状を得ることができない。なお、リン酸は比較的広い濃度範囲で良好な表面性状が得られるが、極端に濃度を高くすることはコスト上昇を招くため、リン酸濃度は９０質量％以下であることが好ましい。
Phosphoric acid: 10 mass% or more When performing electropolishing in a phosphoric acid aqueous solution, the phosphoric acid concentration needs to be 10 mass% or more. When the concentration is lower than this, a liquid film having a high electric resistance cannot be formed on the stainless steel surface, and a smooth surface property cannot be obtained. Phosphoric acid can provide good surface properties in a relatively wide concentration range, but it is preferable that the concentration of phosphoric acid is 90% by mass or less because an extremely high concentration causes an increase in cost.
硫酸：１質量％以上
リン酸水溶液に硫酸を添加すると、表面性状が向上することから、必要に応じて硫酸を加えても良い。効果を得るために必要な硫酸濃度は１質量％以上である。なお、硫酸は過剰に添加しても添加量に見合う効果の上昇は見込めず、コストの上昇を招くのみであるため、硫酸濃度は４０質量％以下であることが好ましい。
Sulfuric acid: When sulfuric acid is added to a phosphoric acid aqueous solution of 1% by mass or more , the surface properties are improved. The sulfuric acid concentration necessary for obtaining the effect is 1% by mass or more. In addition, even if sulfuric acid is added excessively, an increase in the effect corresponding to the addition amount cannot be expected and only an increase in cost is caused. Therefore, the sulfuric acid concentration is preferably 40% by mass or less.
本発明のリチウムイオン二次電池電解液保管容器用フェライト系ステンレス鋼は、上記のように含有成分が制御されていれば、製造方法に制限はない。通常、フェライト系ステンレス鋼に施される熱延，冷延及び焼鈍等を組み合わせて所望板厚の鋼板とした後、適宜の加工手段を用いて所望の電解液保管容器を製造する。また、必要に応じて、容器内面を酸洗及び／又は電解研磨を施す。 The ferritic stainless steel for the lithium ion secondary battery electrolyte storage container of the present invention is not limited in its production method as long as the components are controlled as described above. Usually, after combining the hot rolling, cold rolling, annealing, and the like applied to ferritic stainless steel into a steel plate having a desired thickness, a desired electrolyte storage container is manufactured using an appropriate processing means. Further, the inner surface of the container is pickled and / or electropolished as necessary.
本発明のリチウムイオン二次電池電解液保管容器が収容する電解液は、電解質塩を溶媒に溶かしたものが挙げられる。ここで、電解質塩としては、特に制限されない。具体的には、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＴａＦ６、ＬｉＳｂＦ６、ＬｉＡｌＣｌ４、Ｌｉ２Ｂ１０Ｃｌ１０、ＬｉＩ、ＬｉＢｒ、ＬｉＣｌ、ＬｉＡｌＣｌ、ＬｉＨＦ２、ＬｉＳＣＮ等の無機酸陰イオン塩、ＬｉＣＦ３ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ、ＬｉＢＯＢ（リチウムビスオキサイドボレート）等の有機酸陰イオン塩などが挙げられる。これらの電解質塩は、単独で使用されてもあるいは２種以上の混合物の形態で使用されてもよい。溶媒としては、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート等が挙げられるがこれに限定されない。以上の溶媒を１種もしくは２種以上使用することができる。
As for the electrolyte solution which the lithium ion secondary battery electrolyte storage container of this invention accommodates, what melt | dissolved electrolyte salt in the solvent is mentioned. Here, the electrolyte salt is not particularly limited. Specifically, LiPF 6, LiBF 4, LiClO 4, LiAsF 6, LiTaF 6, LiSbF 6, LiAlCl 4, Li 2
表１に示す成分組成のフェライト系ステンレス鋼を、真空溶製によって３０ｋｇインゴットを作成した。インゴットから４０ｍｍ厚みの熱延用ブロックを採取し、１２３０℃の電気炉内に２ｈ保持した後、熱間圧延にて板厚３ｍｍの熱延板を作成した。熱延板を１０５０℃で焼鈍し、弗酸１．１質量％及び硝酸７．０質量％含む酸洗液を用いて、液温３０℃で５分間の酸洗によって酸化スケールを除去した後、冷間圧延にて板厚１．０ｍｍの冷延板とした。冷延板を結晶粒径が２０〜４０μｍになるよう、９５０〜１０５０℃で焼鈍し、酸洗によって酸化スケールを除去して発明鋼Ｎｏ．１〜９、比較鋼Ｎｏ．１０〜１３を得た。 A 30 kg ingot was produced by vacuum melting the ferritic stainless steel having the composition shown in Table 1. A 40 mm thick hot rolling block was collected from the ingot, held in an electric furnace at 1230 ° C. for 2 hours, and then a hot rolled plate having a thickness of 3 mm was prepared by hot rolling. After annealing the hot-rolled sheet at 1050 ° C. and using a pickling solution containing 1.1% by mass of hydrofluoric acid and 7.0% by mass of nitric acid, the oxide scale was removed by pickling at a temperature of 30 ° C. for 5 minutes. A cold rolled sheet having a thickness of 1.0 mm was formed by cold rolling. The cold-rolled sheet was annealed at 950 to 1050 ° C. so that the crystal grain size was 20 to 40 μm, and the oxide scale was removed by pickling, so 1-9, comparative steel no. 10-13 were obtained.
試験例１
表１に示す板厚１．０ｍｍのフェライト系ステンレス鋼を用い、本発明で規定するとおり、１５ｍｍ×１５ｍｍの小片と４０ｍｍ×４０ｍｍの大片をスポット溶接した。スポット溶接の径はφ５ｍｍのものを用いた。電解液は、エチレンカーボネートとジエチルカーボネートを１：１で混合した溶媒に、１ｍｏｌ／リットルの６弗化リン酸リチウムを加えたものを用いた。電解液１００マイクロリットルを試験片の隙間部に滴下し、その後、５０℃、相対湿度８５％で３時間、５０℃、相対湿度３０％で１時間保持する過程を１００サイクル繰り返した。
Test example 1
Using ferritic stainless steel with a plate thickness of 1.0 mm shown in Table 1, as specified in the present invention, a small piece of 15 mm × 15 mm and a large piece of 40 mm × 40 mm were spot welded. The diameter of spot welding was 5 mm. As the electrolytic solution, a solution obtained by adding 1 mol / liter of lithium hexafluorophosphate to a solvent obtained by mixing ethylene carbonate and diethyl carbonate in a ratio of 1: 1 was used. 100 microliters of the electrolytic solution was dropped into the gap between the test pieces, and then the process of holding at 50 ° C. and a relative humidity of 85% for 3 hours and at 50 ° C. and a relative humidity of 30% for 1 hour was repeated 100 cycles.
試験後の試験片のスポット溶接部に穴を開けて小片と大片を離し、硝酸を用いて除銹を行った後、光学顕微鏡を用いた焦点深度法によって侵食深さを測定した。各鋼種について４検体ずつの試験を行い、各鋼種の最大侵食深さを求めた。その結果を表１および図１に示す。 A hole was made in the spot welded portion of the test piece after the test, the small piece and the large piece were separated from each other, the nitric acid was used to remove the debris, and then the erosion depth was measured by a depth of focus method using an optical microscope. Four specimens were tested for each steel type, and the maximum erosion depth of each steel type was determined. The results are shown in Table 1 and FIG.
Ｃｒ含有量が多いほど、最大侵食深さが小さくなる傾向を示した。特にＣｒ含有量が１６質量％以上になると最大侵食深さは大幅に減少し、ほとんどの鋼種の最大侵食深さが０．２ｍｍ以下であった。ただし、Ａｌ含有量が０．００３質量％未満の場合は、Ｃｒ量が１６質量％以上であっても、最大侵食深さが０．２ｍｍを超えていた。 As the Cr content increased, the maximum erosion depth tended to decrease. In particular, when the Cr content was 16% by mass or more, the maximum erosion depth was greatly reduced, and the maximum erosion depth of most steel types was 0.2 mm or less. However, when the Al content was less than 0.003% by mass, the maximum erosion depth exceeded 0.2 mm even when the Cr content was 16% by mass or more.
板厚２ｍｍの発明鋼１〜３および比較鋼１０〜１２を用い、現在、リチウムイオン二次電池の電解液保管容器として一般的に用いられている形態の容器を作製し、電解液製造所と電池製造所間の電解液の輸送、保管容器として１年間使用した。なお電解液製造所では、容器外面に付着した電解液を洗浄するが、電池製造所において付着した電解液は洗浄せずに放置した。従って、電池製造所から電解液製造所に戻るまでの期間で腐食が進行する状況である。
Using the invention steels 1 to 3 and the
１年経過後に、発明鋼Ｎｏ．１〜Ｎｏ．３、比較鋼Ｎｏ．１０〜Ｎｏ．１２で作製したそれぞれの容器を解体し、腐食状況を調査したところ、発明鋼Ｎｏ．１〜Ｎｏ．３の最大侵食深さはＮｏ．１，２が０．０５ｍｍ、Ｎｏ．３が０．０３ｍｍであった。使用年数に比例して侵食が深くなると想定すると、板厚貫通に至るのは４０年後以上であり、本用途での耐用年数としては満足できるものである。一方、比較鋼の侵食深さはＮｏ．１０が０．７０ｍｍ、Ｎｏ．１１が０．６５ｍｍ、Ｎｏ．１２が０．５０ｍｍであった。板厚貫通まで、２．８〜４年と推察され、耐用年数としては満足できる水準ではなかった。 After one year, the invention steel No. 1-No. 3, comparative steel No. 10-No. 12 was disassembled and the corrosion situation was investigated. 1-No. The maximum erosion depth of No. 3 is no. Nos. 1 and 2 are 0.05 mm. 3 was 0.03 mm. Assuming that erosion deepens in proportion to the service life, it is not less than 40 years after the plate thickness has been penetrated, and the service life in this application is satisfactory. On the other hand, the erosion depth of the comparative steel was No. 10 is 0.70 mm, no. 11 is 0.65 mm, no. 12 was 0.50 mm. It was estimated that 2.8 to 4 years until the plate thickness penetrated, and the service life was not satisfactory.
試験例２
発明鋼１の組成を有し、酸洗を行わなかったこと以外は上記製法と同じ条件で処理された鋼板を用いて、電解液容器を作製し、内面に種々の酸洗および電解研磨を施した。電解液の品質への影響を確認するため、電解液容器に電解液を１週間入れておき、その電解液を用いてリチウムイオン電池を作製し、充放電特性について調査した。
Test example 2
An electrolytic solution container is prepared using a steel plate having the composition of
充放電試験は、１Ａで４Ｖまでの充電、１時間の休止、１Ａで３Ｖまでの放電、１時間の休止を１サイクルとし、５００サイクルまで継続した。１サイクルにおける容量を基準に、５００サイクル後の容量の比率を求め、充放電特性とした。 In the charge / discharge test, charging up to 4 V at 1 A, resting for 1 hour, discharging to 3 V at 1 A, and resting for 1 hour were taken as one cycle and continued up to 500 cycles. Based on the capacity in one cycle, the ratio of the capacity after 500 cycles was determined and used as charge / discharge characteristics.
表２に電解液容器内面の酸洗条件と、その容器で保管した電解液を用いたリチウムイオン電池の充放電特性の関係を示す。本発明の好ましい範囲の酸洗条件では、充放電特性８０〜８２％が得られた。一方、本発明の好ましい範囲外の酸洗条件では、充放電特性が７７％であり、電池性能の低下が早かった。 Table 2 shows the relationship between the pickling conditions on the inner surface of the electrolytic solution container and the charge / discharge characteristics of the lithium ion battery using the electrolytic solution stored in the container. Under the pickling conditions within the preferred range of the present invention, charge / discharge characteristics of 80 to 82% were obtained. On the other hand, under the pickling conditions outside the preferred range of the present invention, the charge / discharge characteristics were 77%, and the battery performance was rapidly reduced.
表３に電解液容器内面の電解研磨条件と、その容器で保管した電解液を用いたリチウムイオン電池の充放電特性の関係を示す。本発明の好ましい範囲の電解研磨条件では、充放電特性８０〜８２％が得られた。一方、本発明の好ましい範囲外の電解研磨条件では、充放電特性が７７％であり、電池性能の低下が早かった。 Table 3 shows the relationship between the electrolytic polishing conditions on the inner surface of the electrolytic solution container and the charge / discharge characteristics of the lithium ion battery using the electrolytic solution stored in the container. Under the electropolishing conditions within the preferred range of the present invention, charge / discharge characteristics of 80 to 82% were obtained. On the other hand, under the electropolishing conditions outside the preferred range of the present invention, the charge / discharge characteristics were 77%, and the battery performance was rapidly reduced.
以上のように、本発明範囲の成分を有するフェライト系ステンレス鋼を用いることで、また任意に酸洗浄や電解研磨を施すことで、安価なフェライト系ステンレス鋼をリチウムイオン電池の電解液保管容器に用いることができる。 As described above, by using a ferritic stainless steel having components within the scope of the present invention, and by optionally performing acid cleaning or electrolytic polishing, an inexpensive ferritic stainless steel can be used as an electrolyte storage container for a lithium ion battery. Can be used.
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