WO2024070493A1 - 電池部品用フェライト系ステンレス鋼材及びその製造方法、並びに電池部品 - Google Patents

電池部品用フェライト系ステンレス鋼材及びその製造方法、並びに電池部品 Download PDF

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WO2024070493A1
WO2024070493A1 PCT/JP2023/031981 JP2023031981W WO2024070493A1 WO 2024070493 A1 WO2024070493 A1 WO 2024070493A1 JP 2023031981 W JP2023031981 W JP 2023031981W WO 2024070493 A1 WO2024070493 A1 WO 2024070493A1
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Prior art keywords
stainless steel
steel material
ferritic stainless
battery
battery components
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PCT/JP2023/031981
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English (en)
French (fr)
Japanese (ja)
Inventor
純一 濱田
篤剛 林
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Nippon Steel Stainless Steel Corp
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Nippon Steel Stainless Steel Corp
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Priority to EP23871733.4A priority Critical patent/EP4541920A4/en
Priority to CN202380062299.0A priority patent/CN119895064A/zh
Priority to KR1020257005257A priority patent/KR20250040037A/ko
Priority to JP2024549929A priority patent/JPWO2024070493A1/ja
Publication of WO2024070493A1 publication Critical patent/WO2024070493A1/ja
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
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    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
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    • C21D8/0221—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
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    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
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    • C21D8/0247—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/004—Dispersions; Precipitations
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors

Definitions

  • the present invention relates to a ferritic stainless steel material for battery components and a manufacturing method thereof, and to battery components.
  • the present invention relates to a ferritic stainless steel material used in battery components of transportation equipment and a manufacturing method thereof, and battery components comprising the ferritic stainless steel material.
  • transportation equipment refers to equipment for transporting luggage or passengers, such as automobiles, two-wheeled vehicles, three-wheeled vehicles, bicycles, buses, and railroad cars.
  • battery components refers to parts that make up a battery, such as a battery case, battery pack, battery module, and battery cover.
  • thermal runaway refers to a phenomenon in which the heat inside the battery becomes uncontrollable due to some cause, causing abnormal heat generation and, in some cases, fire.
  • stainless steel materials containing Cr have superior corrosion resistance compared to ordinary steel, so that it is expected that weight reduction and omission of painting can be achieved by reducing the amount of rust (thickness that allows for rust).
  • Stainless steel materials also have superior heat resistance compared to ordinary steel, so they are resistant to thermal runaway. Therefore, safety can be improved by suppressing ignition and the spread of fire. Therefore, the use of stainless steel materials brings about great benefits such as improved fuel efficiency due to the weight reduction of the vehicle body, simplified painting, and improved safety.
  • electric vehicles and fuel cell vehicles that do not have internal combustion engines are becoming more and more practical.
  • electric vehicles are equipped with large-capacity batteries and run on motor power, and are equipped with many battery components. Since electric vehicles are equipped with multiple batteries, if one battery goes into thermal runaway, it is likely that the other batteries will also go into thermal runaway in a chain reaction, which may lead to a vehicle fire.
  • Patent Document 1 discloses a method for manufacturing a lithium-ion secondary battery case using an austenitic stainless steel foil as a material.
  • Patent Document 2 discloses the application of an austenitic stainless steel sheet to a battery case for mounting on an electric vehicle, which has excellent heat resistance.
  • Patent Document 3 discloses a ferritic stainless steel containing 16.0 to 32.0 mass % of Cr as an electrode material and electrode case for a large-capacity battery.
  • Patent Documents 1 to 3 do not have sufficient impact absorption properties (impact resistance) when used in battery components, and therefore, when the battery is subjected to an impact due to a collision accident or the like, the battery is damaged, and a short circuit occurs in the battery, easily leading to thermal runaway.
  • Patent Document 4 proposes a technique for providing an insulating layer on a laminate seal constituting a secondary battery case.
  • Patent Documents 5 to 7 also propose techniques for suppressing thermal runaway of a battery by providing a member made of mica to a battery component.
  • these techniques have the problem that they cannot prevent damage to battery components, and that the installation of an insulating layer or mica leads to increased costs.
  • these techniques do not improve the shock absorbing properties of stainless steel materials, so it is difficult to reduce the thickness of battery components.
  • Patent Publication No. 6090923 Japanese Patent Application Laid-Open No. 10-188922 JP 2009-167486 A Patent No. 6522736 JP 2022-522369 A International Publication No. 2019/150771 Patent No. 6631726
  • the present invention aims to provide a ferritic stainless steel material for battery components that has excellent battery protection performance and resistance to thermal runaway when the battery is subjected to an impact due to a collision accident or the like, a manufacturing method thereof, and a battery component.
  • a ferritic stainless steel material with a controlled composition and amount of predetermined precipitates can solve the above problems.
  • the inventors have also found that a ferritic stainless steel material with such characteristics can be obtained by annealing and cooling a cold-rolled material with a predetermined composition under specific conditions.
  • the present invention was completed based on these findings.
  • the present invention has a composition that contains, on a mass basis, C: 0.001 to 0.050%, Si: 0.01 to 2.00%, Mn: 0.01 to 2.00%, P: 0.010 to 0.050%, S: 0.0001 to 0.0100%, Cr: 10.0 to 30.0%, N: 0.001 to 0.050%, and further contains one or two selected from Ti: 0.01 to 0.50% and Nb: 0.01 to 0.60%, with the balance being Fe and impurities;
  • the ferritic stainless steel material for battery components contains 0.010 volume % or more of Ti-based precipitates and/or Nb-based precipitates.
  • the present invention also relates to a method for producing a ferritic stainless steel material for battery components, which comprises annealing a cold-rolled material having a composition, by mass, of C: 0.001-0.050%, Si: 0.01-2.00%, Mn: 0.01-2.00%, P: 0.010-0.050%, S: 0.0001-0.0100%, Cr: 10.0-30.0%, N: 0.001-0.050%, and further containing one or two selected from Ti: 0.01-0.50% and Nb: 0.01-0.60%, with the balance being Fe and impurities, at 850-1050°C, and then cooling to 800°C at a rate of 10°C/sec or less.
  • the present invention relates to a battery component comprising a ferritic stainless steel material for battery components.
  • the present invention provides a ferritic stainless steel material for battery components that has excellent battery protection performance and resistance to thermal runaway when the battery is subjected to an impact due to a collision accident, etc., a manufacturing method thereof, and a battery component.
  • 1 is a graph showing the relationship between strain and flow stress when a tensile test was conducted at a strain rate of 103 /sec for a ferritic stainless steel material containing 0.010 volume % of Ti-based precipitates and/or Nb-based precipitates and a ferritic stainless steel material not containing Ti-based precipitates and/or Nb-based precipitates.
  • various ferritic stainless steel materials were produced and analyzed and examined in detail, using the flow stress at 10% strain when a tensile test was performed at a strain rate of 103 /sec, assuming an impact due to a collision accident, as an evaluation of the impact absorption characteristics during high-speed deformation, and the Young's modulus at 900°C as an evaluation of high-temperature rigidity.
  • the composition of the ferritic stainless steel material and the amount of predetermined precipitates it is possible to improve the impact absorption characteristics during high-speed deformation and the high-temperature rigidity, which led to the completion of the present invention.
  • ferritic stainless steel material for battery components contains C: 0.001-0.050%, Si: 0.01-2.00%, Mn: 0.01-2.00%, P: 0.010-0.050%, S: 0.0001-0.0100%, Cr: 10.0-30.0%, N: 0.001-0.050%, and further contains one or two types selected from Ti: 0.01-0.50% and Nb: 0.01-0.60%, with the balance being Fe and impurities.
  • impurities refers to components that are mixed in due to various factors in raw materials such as ores and scraps and manufacturing processes during industrial production of ferritic stainless steel materials, and are acceptable within a range that does not adversely affect the present invention.
  • impurities include unavoidable impurities.
  • impurities include O, As, Pb, etc. It is preferable to reduce impurities as much as possible.
  • stainless steel material refers to a material formed from stainless steel, and the shape of the material is not particularly limited. Examples of the material shape include a plate shape (including a strip shape), a rod shape, a tube shape, and the like.
  • the material may be various shaped steels having a cross-sectional shape such as a T-shape or an I-shape.
  • ferritic means that the metal structure at room temperature is mainly ferritic. Therefore, “ferritic” also includes those that contain small amounts of phases other than ferritic (for example, austenite phase or martensite phase). However, “ferritic” does not include a multi-phase structure of ferritic and austenite phases, a multi-phase structure of ferritic and martensite phases, or a multi-phase structure of ferritic, austenite, and martensite phases. Stainless steel materials with these multi-phase structures have high strength, but are insufficient in shock absorption characteristics (flow stress during high-speed deformation) and workability during high-speed deformation.
  • the ferritic stainless steel material according to an embodiment of the present invention has the following composition: Ni: 0.01 to 2.00%, Al: 0.001 to 1.000%, Cu: 0.01 to 2.00%, Mo: 0.01 to 3.00%, V: 0.01 to 0.50%, Zr: 0.01 to 0.50%, B: 0.0002 to 0.0050%, Ca: 0.0005 to 0.0100%, W: 0.10 to 3.00%, Sn: 0.
  • It may further contain one or more selected from the group consisting of 0.01 to 0.50%, Co: 0.03 to 0.30%, Mg: 0.0002 to 0.0100%, Sb: 0.005 to 0.300%, REM: 0.002 to 0.200%, Ga: 0.0002 to 0.3000%, Ta: 0.001 to 1.000%, Hf: 0.001 to 1.000%, and Bi: 0.001 to 0.020%.
  • 0.01 to 0.50% Co: 0.03 to 0.30%
  • Mg 0.0002 to 0.0100%
  • Sb 0.005 to 0.300%
  • REM 0.002 to 0.200%
  • Ga 0.0002 to 0.3000%
  • Ta 0.001 to 1.000%
  • Hf 0.001 to 1.000%
  • Bi 0.001 to 0.020%.
  • C is an element that reduces corrosion resistance and heat resistance
  • the C content is set to 0.050% or less.
  • the lower limit of the C content is set to 0.001%.
  • the lower limit of the C content is preferably 0.003% or more.
  • the upper limit of the C content is preferably 0.010% or less.
  • the C content is more preferably 0.003 to 0.008%.
  • Si is a deoxidizing element.
  • Si is a solid solution strengthening element and is an element effective in improving the shock absorbing properties (flow stress during high speed deformation) during high speed deformation, so the Si content is set to 0.01% or more.
  • the upper limit of the Si content is set to 2.00%.
  • the Si content is preferably 0.05 to 0.90%.
  • the Si content is more preferably 0.10 to 0.40%.
  • Mn is a deoxidizing element.
  • Mn is a solid solution strengthening element and is an element effective in improving the shock absorption characteristics (flow stress during high speed deformation) during high speed deformation, so the Mn content is set to 0.01% or more.
  • the upper limit of the Mn content is set to 2.00%.
  • the Mn content is preferably 0.10 to 1.00%.
  • the Mn content is more preferably 0.20 to 0.50%.
  • ⁇ P: 0.010 to 0.050%> P reduces workability, corrosion resistance, manufacturability, etc., so the less the better. If the P content is too high, coarse phosphides are generated, which become the starting point for void generation during high-speed deformation, so the upper limit of the P content is set to 0.050%. On the other hand, the formation of fine FeTiP or FeNbP leads to improvement of the shock absorption characteristics (flow stress during high-speed deformation) during high-speed deformation, so the lower limit of the P content is set to 0.010%. In addition, taking into account the refining cost and workability, the P content is preferably 0.020 to 0.030%.
  • Cr is an element added to improve corrosion resistance and heat resistance.
  • the Cr content is set to 10.0% or more in order to eliminate painting and improve high-temperature rigidity.
  • the upper limit of the Cr content is set to 30.0%.
  • the Cr content is preferably 11.0 to 18.0%.
  • N is an element that reduces corrosion resistance and heat resistance
  • the N content is set to 0.050% or less.
  • the lower limit of the N content is set to 0.001%.
  • the upper limit of the N content is preferably 0.010% or less.
  • the N content is more preferably 0.003 to 0.008%.
  • Ti and Nb combine with C and N to prevent the formation of coarse Cr carbonitrides, thereby preventing intergranular corrosion, and also promote the development of ⁇ 111 ⁇ texture, contributing to the improvement of workability (e.g., deep drawability).
  • Ti and Nb are also elements necessary for generating Ti-based precipitates and Nb-based precipitates that are effective in improving the shock absorption characteristics (flow stress during high-speed deformation) during high-speed deformation.
  • Ti-based precipitates and Nb-based precipitates means carbides and nitrides of Ti and Nb, as well as phosphides (FeTiP, FeNbP) and sulfides (TiS, Ti 4 C 2 S 2 ).
  • the Ti content is set to 0.01% or more and the Nb content is set to 0.01% or more.
  • excessive addition of Ti and Nb causes the Ti-based precipitates and Nb-based precipitates to become too coarse, resulting in a decrease in toughness.
  • the upper limit of the Ti content is set to 0.50%, and the upper limit of the Nb content is set to 0.60%.
  • the Ti content and the Nb content are both preferably 0.05 to 0.30% or less.
  • the Ti content and the Nb content are both more preferably 0.05 to 0.20%.
  • Ni is an element that contributes to high strength and is effective in improving the shock absorption properties (flow stress during high speed deformation) during high speed deformation, and is added in an amount of 0.01% or more as necessary.
  • the upper limit of the Ni content is set to 2.00%.
  • the Ni content is preferably 0.10 to 1.00%.
  • the Ni content is more preferably 0.20 to 0.50%.
  • Al is an element added as a deoxidizing element. In order to efficiently exert this effect, 0.001% or more is added as necessary. Furthermore, Al is also an element that is effective in improving workability by forming nitrides, increasing strength by solid solution strengthening, and improving oxidation resistance. However, excessive addition of Al leads to a decrease in high-temperature rigidity, the occurrence of surface defects, a decrease in weldability, and a decrease in ductility due to coarse AlN. Therefore, the upper limit of the Al content is set to 1.000%. In addition, in consideration of deoxidizing efficiency and toughness, the Al content is preferably 0.020 to 0.500%. Furthermore, in consideration of weldability, the Al content is more preferably 0.020 to less than 0.100%.
  • ⁇ Cu 0.01 to 2.00%> Cu contributes to improving corrosion resistance and improving high-temperature rigidity and strength by precipitation of ⁇ -Cu, and is added in an amount of 0.01% or more as necessary. However, if the Cu content is too high, ductility decreases significantly, so the upper limit of the Cu content is set to 2.00%. In addition, in consideration of oxidation resistance and component costs, the Cu content is preferably 0.05 to 1.50%. Furthermore, in consideration of toughness and weldability, the Cu content is more preferably 0.10 to 0.50%.
  • Mo is an element that improves corrosion resistance.
  • Mo is a solid solution strengthening element, and is effective in improving the shock absorption characteristics (flow stress during high-speed deformation) during high-speed deformation. Therefore, Mo is added in an amount of 0.01% or more as necessary.
  • the upper limit of the Mo content is set to 3.00%.
  • the Mo content is preferably 0.10 to 1.50%.
  • the Mo content is more preferably 0.10 to 1.20%.
  • V and Zr are elements that combine with C and N, like Ti and Nb, and suppress the generation of coarse Cr carbonitrides.
  • V and Zr are also effective elements for the generation of fine precipitates (Zr(C,N), V(C,N)) for improving the shock absorption characteristics (flow stress during high-speed deformation) during high-speed deformation. Therefore, V and Zr are added in an amount of 0.01% or more as necessary.
  • the upper limits of the V content and the Zr content are both set to 0.50%.
  • the V content and the Zr content are both preferably 0.05 to 0.30%. Furthermore, in consideration of the shock absorption characteristics and bendability during high-speed deformation of the weld, the V content and the Zr content are both more preferably 0.1 to 0.2%.
  • B is an element that is effective in increasing strength, and also suppresses secondary processing cracks.
  • B forms borides, and may be effective in improving the shock absorption characteristics (flow stress during high-speed deformation) during high-speed deformation. Therefore, B is added at 0.0002% or more as necessary.
  • the upper limit of the B content is set to 0.0050%.
  • the B content is preferably 0.0002 to 0.0020%.
  • the B content is more preferably 0.0005 to 0.0010%.
  • Ca is added in an amount of 0.0005% or more as necessary to fix S and improve hot workability.
  • the upper limit of the Ca content is set to 0.0100%.
  • the Ca content is preferably 0.0005 to 0.0010%.
  • W is an element that improves corrosion resistance and also acts as a solid solution strengthening element. Therefore, 0.10% or more is added depending on the corrosion resistance level in the usage environment. However, since excessive addition of W leads to a decrease in workability and toughness and an increase in cost, the upper limit of the W content is set to 3.00%.
  • the W content is preferably 0.10 to 1.50%.
  • Sn contributes to improving corrosion resistance and high-temperature strength, so 0.01% or more is added as necessary.
  • excessive addition of Sn may cause slab cracking during manufacturing, and grain boundary cracking during processing (e.g., hole expansion) becomes prominent. Therefore, the upper limit of the Sn content is set to 0.50%.
  • the Sn content is preferably 0.01 to 0.30%.
  • Co contributes to improving high-temperature strength, so 0.03% or more is added as necessary.
  • the upper limit of the Co content is set to 0.30%.
  • the Co content is preferably 0.03 to 0.10%.
  • Mg is an element added as a deoxidizing element.
  • Mg contributes to improving manufacturability by refining ferrite grains, improving surface defects called ridging, and improving the workability of welds.
  • the Mg content is set to 0.0002% or more.
  • the upper limit of the Mg content is set to 0.0100%.
  • the Mg content is preferably 0.0002 to 0.0020%.
  • Sb is an element that segregates at grain boundaries to increase high-temperature strength.
  • the Sb content is set to 0.005% or more.
  • the upper limit of the Sb content is set to 0.300%.
  • the Sb content is preferably 0.030 to 0.200%, and more preferably 0.050 to 0.100%.
  • REM 0.002 to 0.200%> REM (rare earth elements) are effective in improving oxidation resistance, and are added at 0.002% or more as necessary. However, if REM is added excessively, the effect saturates and REM granules cause a decrease in corrosion resistance and hole expandability, so the upper limit of the REM content is set to 0.200%. Considering workability and manufacturing costs, the REM content is preferably 0.002 to 0.100%.
  • the REM follows the general definition. That is, REM refers to two elements, scandium (Sc) and yttrium (Y), and 15 elements (lanthanoids) from lanthanum (La) to lutetium (Lu). REM may be added alone or in the form of a mixture.
  • Ga is an element that is added as necessary to improve corrosion resistance and suppress hydrogen embrittlement.
  • the lower limit of the Ga content is set to 0.0002%.
  • the Ga content is preferably 0.0020% or more.
  • excessive addition of Ga causes the generation of coarse sulfides, which reduces workability (e.g., hole expandability), so the upper limit of the Ga content is set to 0.3000%.
  • Ta and Hf are elements effective for improving high-temperature strength, and are added as necessary.
  • the Ta content and Hf content are both set to 0.001 to 1.000%. From the viewpoint of improving high-temperature strength, the Ta content and Hf content are preferably 0.100% or less, and more preferably 0.010% or less.
  • Bi is an element effective in improving machinability and is added as necessary.
  • the Bi content is set to 0.001 to 0.020%. From the viewpoint of improving machinability, the Bi content is preferably 0.015% or less.
  • the ferritic stainless steel material according to the embodiment of the present invention contains 0.010 vol.% or more of Ti-based precipitates and/or Nb-based precipitates. That is, the ferritic stainless steel material according to the embodiment of the present invention may have an amount of Ti-based precipitates of 0.010 vol.% or more, an amount of Nb-based precipitates of 0.010 vol.% or more, and a total amount of Ti-based precipitates and Nb-based precipitates of 0.010 vol.% or more. By controlling the amount of Ti-based precipitates and/or Nb-based precipitates within such a range, it is possible to improve the impact absorption characteristics and high-temperature rigidity during high-speed deformation.
  • the upper limit of the amount of Ti-based precipitates and/or Nb-based precipitates is not particularly limited, but if it is too large, it may cause molding defects due to void formation. From the viewpoint of suppressing this problem, it is preferable that the amount of Ti-based precipitates and/or Nb-based precipitates is 0.200 vol.% or less. In addition, when considering low-temperature toughness and weldability, the amount of Ti-based precipitates and/or Nb-based precipitates is more preferably 0.020 to 0.100 volume percent.
  • the amount of Ti-based precipitates and/or Nb-based precipitates in ferritic stainless steel materials can be determined by observing the cross section of the ferritic stainless steel material under a microscope and calculating the area ratio of the area containing Ti-based precipitates and/or Nb-based precipitates to the entire structure according to the point counting method specified in JIS G0555:2003.
  • the particle size of the Ti-based precipitates and/or Nb-based precipitates is not particularly limited, but is preferably 10 ⁇ m or less, more preferably 9 ⁇ m or less. By controlling the particle size of the Ti-based precipitates and/or Nb-based precipitates within this range, it is possible to improve the shock absorption characteristics during high-speed deformation and high-temperature rigidity, as well as the corrosion resistance by suppressing the formation of voids during forming.
  • the lower limit of the particle size of the Ti-based precipitates and/or Nb-based precipitates is not particularly limited, but is typically 0.1 ⁇ m, preferably 1 ⁇ m.
  • the particle size of the Ti-based precipitates and/or Nb-based precipitates can be measured by observing the cross section of the ferritic stainless steel material with a scanning electron microscope.
  • the particle size of the Ti-based precipitates and/or Nb-based precipitates is calculated as the diameter of a circle having the same area.
  • the ferritic stainless steel material according to the embodiment of the present invention preferably has a flow stress of 500 MPa or more at 10% strain when a tensile test is carried out at a strain rate of 10 3 /sec.
  • the flow stress at 10% strain when a tensile test is performed at a strain rate of 103 /sec is an index showing the shock absorbing properties during high-speed deformation assuming an impact due to a collision accident or the like. If this flow stress is 500 MPa or more, it can be said that the shock absorbing properties during high-speed deformation are excellent, and the collision safety of battery components of general automobiles can be ensured.
  • this flow stress is more preferably 550 MPa or more, and even more preferably 600 MPa or more.
  • FIG. 1 shows the results of a tensile test performed at a strain rate of 10 3 /sec on a ferritic stainless steel material containing 0.010 volume% of Ti-based precipitates and/or Nb-based precipitates (referred to as an "invention example") and a ferritic stainless steel material not containing Ti-based precipitates and/or Nb-based precipitates (referred to as a "comparison example").
  • FIG. 1 is a graph showing the relationship between strain (x-axis) and flow stress (y-axis). Both the ferritic stainless steel materials of the invention example and the comparison example had a composition containing 17%Cr-0.01%C-0.01%N.
  • the examples of the invention have a high flow stress at 10% strain of 500 MPa or more and are excellent in shock absorption properties during high-speed deformation, whereas the comparative examples have a flow stress at 10% strain of less than 500 MPa.
  • the strain rate is extremely high, such as 103 /sec, as occurs in a collision accident, the presence of Ti-based precipitates and/or Nb-based precipitates effectively prevents dislocation movement, leading to an increase in flow stress.
  • the ferritic stainless steel material according to the embodiment of the present invention preferably has a Young's modulus at 900° C. of 80 GPa or more.
  • the Young's modulus at 900°C is an index representing high-temperature rigidity.
  • the inside of the destroyed battery instantaneously reaches a high temperature of about 900°C, so that the battery components constituting the other batteries are also exposed to high temperatures.
  • the Young's modulus at 900°C is less than 80 GPa, the battery components are deformed and are likely to develop into thermal runaway.
  • the Young's modulus at 900°C is 80 GPa or more, the deformation of the battery components can be suppressed and thermal runaway can be suppressed.
  • the Young's modulus at 900°C is more preferably 90 GPa or more.
  • the Young's modulus at 900° C. can be determined by a resonance method in accordance with the method defined in JIS Z2280:1993.
  • the ferritic stainless steel material according to the embodiment of the present invention preferably has a breaking elongation at room temperature (25° C.) of 30% or more.
  • the breaking elongation at room temperature is an index of processability. By making the breaking elongation at room temperature 30% or more, the processability into battery components having various shapes is ensured.
  • the upper limit of the breaking elongation at room temperature is not particularly limited, but is, for example, 50%.
  • the breaking elongation at room temperature can be determined by conducting a tensile test in accordance with JIS Z2241:2011 using a JIS No. 13B test piece taken so that the rolling direction of the ferritic stainless steel material is parallel to the parallel portion.
  • the maximum pitting depth is preferably less than 200 ⁇ m.
  • the maximum pit depth is an index representing corrosion resistance. By making the maximum pit depth less than 200 ⁇ m, it can be said that the corrosion resistance is excellent.
  • the maximum pit depth can be determined by carrying out 30 cycles of the JASO-CCT test on a ferritic stainless steel material, subjecting it to a rust removing treatment, and then measuring it by a focal depth method using a microscope.
  • the thickness of the ferritic stainless steel material according to the embodiment of the present invention is not particularly limited and may be appropriately set according to the characteristics of the product in which the ferritic stainless steel material is used.
  • the thickness of the ferritic stainless steel material is preferably 1.0 mm or less.
  • the thickness of the ferritic stainless steel material is more preferably 0.1 mm or more.
  • the thickness of the ferritic stainless steel material is even more preferably 0.2 to 0.8 mm.
  • the thickness of the ferritic stainless steel material is even more preferably 0.3 to 0.6 mm.
  • the ferritic stainless steel material according to the embodiment of the present invention has excellent shock absorption properties and high-temperature rigidity during high-speed deformation because the composition and the amount of the specified precipitates are controlled as described above. Therefore, the ferritic stainless steel material according to the embodiment of the present invention has excellent battery protection performance and resistance to thermal runaway when the battery is subjected to an impact due to a collision accident or the like. In addition, the ferritic stainless steel material according to the embodiment of the present invention contributes to reducing the cost of battery components because it does not require the formation of an insulating layer or the application of mica, which was required in conventional technology to suppress thermal runaway of the battery due to an impact.
  • the manufacturing method of the ferritic stainless steel material according to the embodiment of the present invention is not particularly limited as long as it is a method capable of manufacturing a ferritic stainless steel material having the above-mentioned characteristics.
  • a method for producing a ferritic stainless steel material according to an embodiment of the present invention is carried out by annealing a cold-rolled material having the above composition at 850 to 1050°C, and then cooling it to 800°C at a cooling rate of 10°C/sec or less. By controlling the conditions in this way, a ferritic stainless steel material having the above characteristics can be produced. After annealing and cooling as described above, pickling treatment may be carried out as necessary.
  • pickling treatment may be carried out as necessary.
  • Cold-rolled material can be manufactured by conventional methods. Specifically, first, stainless steel having the above composition is melted and forged or cast, and then hot-rolled to obtain hot-rolled material. Next, the hot-rolled material is annealed, pickled, and cold-rolled in sequence to obtain cold-rolled material.
  • each step can be performed using existing equipment, and the conditions can be adjusted appropriately depending on the composition of the stainless steel, and are not particularly limited.
  • existing treatments for example, surface polishing, temper rolling, treatment using a tension leveler, etc. may be performed as necessary.
  • the cold-rolled material obtained as described above is annealed at 850 to 1050°C.
  • annealing temperature is preferably 880 to 1000°C.
  • the grain size number specified in JIS G0551:2013 can be controlled to 5 to 9, preferably 6 to 8.
  • the annealing can be performed in a normal annealing device, such as a continuous annealing line.
  • the cold-rolled material after annealing is usually cooled by air cooling, but in order to generate 0.010 volume % or more of Ti-based precipitates and/or Nb-based precipitates (hereinafter, these will be abbreviated as "precipitates") during the cooling process, the cooling rate to 800°C is set to 10°C/sec or less. By cooling under such conditions, the precipitation of precipitates can be promoted. There is no particular limit to the lower limit of this cooling rate, but if it is too slow, the precipitates may become too coarse, leading to a deterioration in toughness. Therefore, it is preferable to set the lower limit of this cooling rate to 3°C/sec. Furthermore, considering productivity and the shape of the steel material, it is more preferable that this cooling rate be 4 to 8°C/sec.
  • the cold-rolled material after annealing cooled to 800°C is preferably cooled to 400°C (i.e., in the temperature range from 800°C to 400°C) at a cooling rate of more than 10°C/sec, more preferably at 12°C/sec or more, and even more preferably at 15°C/sec or more.
  • a cooling rate of more than 10°C/sec, more preferably at 12°C/sec or more, and even more preferably at 15°C/sec or more.
  • the battery component according to the embodiment of the present invention includes the above-mentioned ferritic stainless steel material. Since the above-mentioned ferritic stainless steel material has excellent shock absorption properties during high-speed deformation and high-temperature rigidity, the battery component has excellent battery protection performance and resistance to thermal runaway when the battery is subjected to an impact due to a collision accident or the like.
  • Battery parts are not particularly limited, but examples thereof include a battery case, a battery pack, a battery module, and a battery cover.
  • a ferritic stainless steel sheet was prepared according to the following procedure. Stainless steel having the composition shown in Tables 1 and 2 was melted and hot rolled to obtain a hot rolled sheet having a thickness of 3.8 mm, which was then pickled to obtain a hot rolled pickled sheet. The hot rolled pickled sheet was then cold rolled to obtain a cold rolled sheet having a thickness of 0.6 mm. The cold rolled sheet was then annealed and cooled under the conditions shown in Tables 3 and 4, and then pickled to obtain a cold rolled annealed sheet (ferritic stainless steel sheet).
  • the cold-rolled annealed sheets obtained above were subjected to the following evaluations.
  • ⁇ Amount of Ti-based precipitates and/or Nb-based precipitates (hereinafter, abbreviated as "precipitates")>
  • the cross section of the cold-rolled annealed sheet was observed under a microscope, and the amount of precipitates was determined from the area ratio of the area where the precipitates existed to the entire structure.
  • the cold-rolled annealed sheet was filled with resin so that the thickness direction cross section parallel to the rolling direction of the sheet was the observation surface, and after mirror polishing, the inclusions at 1/4 to 3/4 of the thickness were observed at a magnification of 400 times using an optical microscope.
  • 60 fields of view were observed using an optical microscope with a 20 x 20 grid attached to the measurement lens, and the area ratio of the inclusions in the grid was calculated, which was the amount of precipitates (volume %).
  • ⁇ Particle size of precipitates> The grain size of the precipitates was measured by filling the cold-rolled annealed sheet with resin so that the thickness direction cross section parallel to the rolling direction was the observation surface, mirror polishing, and then observing the precipitates at 1/4 to 3/4 of the thickness at a magnification of 3000 times using a scanning electron microscope. Observation was performed in 10 fields of view, the area of the largest precipitate was calculated, and the circle equivalent diameter was determined as the grain size of the precipitate.
  • the precipitates were analyzed by EDS attached to a scanning electron microscope, and were determined to be precipitates when the Ti and/or Nb content of the precipitate was equal to or greater than the content of the base material.
  • the Young's modulus at 900°C was determined by a resonance method in accordance with the method specified in JIS Z2280: 1993. Specifically, a test piece for measurement, 60 mm long in the rolling direction and 10 mm wide in the width direction, was taken from the cold-rolled annealed sheet, and measured at 900°C by a resonance method using an elastic modulus measuring device (EG-HT elastic modulus measuring device manufactured by Nippon Technoplus Co., Ltd.).
  • EG-HT elastic modulus measuring device manufactured by Nippon Technoplus Co., Ltd.
  • ⁇ Corrosion resistance (maximum pitting depth)> A test piece for measurement having a length of 150 mm in the rolling direction and 75 mm in the width direction was taken from the cold-rolled annealed sheet. Next, 30 cycles of JASO-CCT test (according to the conditions of M609-91, salt spray (35°C, concentration 5%, 2 hours), drying (60°C, 25% RH, 4 hours), and wetting (50°C, 95% RH, 2 hours) are one cycle) were performed, and then rust removal treatment was performed. Next, the maximum pitting depth was measured by the focal depth method using a microscope. In this evaluation, a maximum pitting depth of less than 200 ⁇ m was marked as ⁇ , and a maximum pitting depth of 200 ⁇ m or more was marked as ⁇ .
  • the cold-rolled annealed sheets of Examples 1 to 24 had high flow stress at 10% strain when a tensile test was performed at a strain rate of 103 /sec, and high Young's modulus at 900°C, and were excellent in impact absorption properties during high-speed deformation and high-temperature rigidity. Furthermore, the cold-rolled annealed sheets of Examples 1 to 24 also had good results in fracture elongation and corrosion resistance (maximum pitting depth) at room temperature, and were also excellent in workability and corrosion resistance.
  • the cold-rolled annealed sheets of Comparative Examples 1 to 4 had inappropriate annealing temperature or cooling rate conditions and too little precipitate, so that either or both of the flow stress at 10% strain and Young's modulus at 900 ° C. were low when a tensile test was performed at a strain rate of 10 3 / s.
  • the cold-rolled annealed sheets of Comparative Examples 5 to 31 did not satisfy the predetermined composition, and in some Comparative Examples, the annealing temperature was also inappropriate, so either or both of the flow stress at 10% strain and Young's modulus at 900 ° C. were low when a tensile test was performed at a strain rate of 10 3 /s.
  • the cold-rolled annealed sheets of Comparative Examples 3 to 31 had insufficient results in either or both of the fracture elongation and corrosion resistance (maximum pitting depth) at room temperature.
  • the present invention can provide a ferritic stainless steel material for battery components that has excellent battery protection performance and resistance to thermal runaway when the battery is subjected to an impact due to a collision accident or the like, a manufacturing method thereof, and a battery component.
  • the present invention can be configured as follows.
  • the ferritic stainless steel material for battery components described in [1] further contains one or more selected from the following: 0%, Mg: 0.0002-0.0100%, Sb: 0.005-0.300%, REM: 0.002-0.200%, Ga: 0.0002-0.3000%, Ta: 0.001-1.000%, Hf: 0.001-1.000%, Bi: 0.001-0.020%.
  • [5] having the following characteristics: The ferritic stainless steel material for battery components according to any one of [1] to [4], which satisfies one or more of the following: (1) a breaking elongation at room temperature of 30% or more; and (2) a maximum pitting depth of less than 200 ⁇ m.
  • a ferritic stainless steel material for battery components according to any one of [1] to [5], having a thickness of 1.0 mm or less.
  • a method for producing a ferritic stainless steel material for battery components comprising annealing a cold-rolled material having a composition, by mass, of C: 0.001-0.050%, Si: 0.01-2.00%, Mn: 0.01-2.00%, P: 0.010-0.050%, S: 0.0001-0.0100%, Cr: 10.0-30.0%, N: 0.001-0.050%, Ti: 0.01-0.50%, Nb: 0.01-0.60%, and the balance being Fe and impurities, at 850-1050°C, followed by cooling to 800°C at a rate of 10°C/sec or less.
  • the cold-rolled material has, by mass, the following composition: Ni: 0.01-2.00%, Al: 0.001-1.000%, Cu: 0.01-2.00%, Mo: 0.01-3.00%, V: 0.01-0.50%, Zr: 0.01-0.50%, B: 0.0002-0.0050%, Ca: 0.0005-0.0100%, W: 0.10-3.00%, Sn: 0.01-0.50%, Co: 0.03-0.
  • a battery component comprising the ferritic stainless steel material for battery components described in any one of [1] to [6].

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