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 PDFInfo
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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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- C21D2211/00—Microstructure comprising significant phases
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- 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
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- 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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Abstract
Description
一方、Crを含有するステンレス鋼材は、普通鋼に比べて耐食性に優れているため、錆代(錆を見込んだ厚み)の低減による軽量化、塗装省略化が期待される。また、ステンレス鋼材は、普通鋼に比べて耐熱性にも優れているため、熱暴走に対する耐性を有している。それ故、発火や延焼の抑制によって安全性を向上させることができる。したがって、ステンレス鋼材を用いることにより、車体軽量化による燃費向上、塗装簡略化、安全性の向上などのメリットが大きくなる。
例えば、電池部品に用いられるステンレス鋼材として、特許文献1には、オーステナイト系ステンレス鋼箔を素材としたリチウムイオン2次電池用ケースの製造方法が開示されている。また、特許文献2には、耐熱性に優れた電気自動車搭載用電池ケースにオーステナイト系ステンレス鋼板を適用することが開示されている。さらに、特許文献3には大容量バッテリーの電極材及び電極ケースとしてCrを16.0~32.0質量%添加したフェライト系ステンレス鋼が開示されている。
しかしながら、特許文献1~3に開示されたステンレス鋼材は、電池部品に用いた場合、衝撃吸収特性(耐衝撃性)が十分でない。そのため、衝突事故などによって電池に衝撃が加えられると、電池が破損し、電池内で短絡が発生して熱暴走に至り易い。
しかしながら、これらの技術では、電池部品の破損を抑制することができないとともに、絶縁層やマイカの設置によってコストアップに繋がるという課題がある。また、これらの技術は、ステンレス鋼材の衝撃吸収特性を向上させるものではないため、電池部品の厚みを低減することも難しい。
このような状況の下、本発明は、衝突事故などによって電池に衝撃が加えられた際に、電池の保護性能及び熱暴走に対する耐性に優れる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、並びに電池部品を提供することを目的とする。
Ti系析出物及び/又はNb系析出物を0.010体積%以上含む、電池部品用フェライト系ステンレス鋼材である。
本発明では、高速変形時の衝撃吸収特性の評価として、衝突事故などによる衝撃を想定し、103/秒の歪速度で引張試験を行った際の10%歪における流動応力を用いるとともに、高温剛性の評価として、900℃におけるヤング率をそれぞれ用い、様々なフェライト系ステンレス鋼材を作製し、詳細な分析及び検討を行った。その結果、フェライト系ステンレス鋼材の組成及び所定の析出物の量を制御することにより、高速変形時の衝撃吸収特性及び高温剛性を向上させ得ることを見出し、本発明を完成するに至った。
なお、本明細書において成分に関する「%」表示は、特に断らない限り「質量%」を意味する。
本発明の実施形態に係る電池部品用フェライト系ステンレス鋼材(以下、「フェライト系ステンレス鋼材」と略すことがある)は、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%を含有し、Ti:0.01~0.50%及びNb:0.01~0.60%から選択される1種又は2種を更に含有し、残部がFe及び不純物からなる組成を有する。
また、本明細書において「ステンレス鋼材」とは、ステンレス鋼から形成された材料のことを意味し、その材形は特に限定されない。材形の例としては、板状(帯状を含む)、棒状、管状などが挙げられる。また、断面形状がT形、I形などの各種形鋼であってもよい。
以下、各成分について詳細に説明する。
Cは、耐食性及び耐熱性を低下させる元素であるため、C含有量を0.050%以下とする。ただし、Cの過度な低減は精錬コストの増加に繋がることから、C含有量の下限を0.001%とする。また、高速変形時の衝撃吸収特性(高速変形時の流動応力)の観点から、C含有量の下限は0.003%以上が好ましい。また、溶接性の観点から、C含有量の上限は0.010%以下が好ましい。さらに、製造性及び加工性を考慮すると、C含有量は0.003~0.008%がより好ましい。
Siは、脱酸元素である。また、Siは、固溶強化元素であり、高速変形時の衝撃吸収特性(高速変形時の流動応力)の向上に有効な元素であるため、Si含有量を0.01%以上とする。ただし、Siの過度な添加は、延性の急激な低下に繋がるため、Si含有量の上限を2.00%とする。また、耐食性及び製造性を考慮すると、Si含有量は0.05~0.90%が好ましい。さらに、溶接性及び靭性を考慮すると、Si含有量は0.10~0.40%がより好ましい。
Mnは、脱酸元素である。また、Mnは、固溶強化元素であり、高速変形時の衝撃吸収特性(高速変形時の流動応力)の向上に有効な元素であるため、Mn含有量を0.01%以上とする。ただし、Mnの過度な添加は、耐食性の低下に繋がるため、Mn含有量の上限を2.00%とする。また、耐酸化性及び強度を考慮すると、Mn含有量は0.10~1.00%が好ましい。さらに、製造性及び溶接性を考慮すると、Mn含有量は0.20~0.50%がより好ましい。
Pは、加工性、耐食性、製造性などを低下させるため、少ないほど望ましい。P含有量が多すぎると、粗大なリン化物が生成し、高速変形時にボイド生成の起点となるため、P含有量の上限を0.050%とする。一方、微細なFeTiPやFeNbPの形成は、高速変形時の衝撃吸収特性(高速変形時の流動応力)の向上に繋がることから、P含有量の下限を0.010%とする。また、精錬コスト及び加工性を考慮すると、P含有量は0.020~0.030%が好ましい。
Sは、加工性、耐食性、製造性などを低下させるため、少ないほど望ましい。S含有量が多すぎると、粗大な硫化物が生成し、高速変形時にボイド生成の起点となるため、S含有量の上限を0.0100%とする。一方、微細なTiSやTi4C2S2の形成は、高速変形時の衝撃吸収特性(高速変形時の流動応力)の向上に繋がることから、S含有量の下限を0.0001%とする。また、精錬コスト及び溶接性を考慮すると、S含有量は0.0005~0.0020%が好ましい。
Crは、耐食性及び耐熱性を向上させるために添加される元素である。特に、塗装などの省略及び高温剛性の向上のため、Cr含有量を10.0%以上とする。一方、Cr含有量が多すぎると、靭性が著しく低下するため、Cr含有量の上限を30.0%とする。また、製造性、コスト、溶接部の耐食性、高速変形時の衝撃吸収特性を考慮すると、Cr含有量は11.0~18.0%が好ましい。
Nは、耐食性及び耐熱性を低下させる元素であるため、N含有量を0.050%以下とする。ただし、Nの過度な低減は精錬コストの増加に繋がることから、N含有量の下限を0.001%とする。また、高速変形時の衝撃吸収特性の観点から、N含有量の下限は0.003%以上が好ましい。また、溶接性の観点から、N含有量の上限は0.010%以下が好ましい。さらに、製造性及び加工性を考慮すると、N含有量は0.003~0.008%がより好ましい。
Ti及びNbは、C及びNと結合し、粗大なCr炭窒化物が生成されるのを抑制することで粒界腐食を防止する他、{111}集合組織の発達を促し、加工性(例えば、深絞り性)の向上に寄与する。また、Ti及びNbは、高速変形時の衝撃吸収特性(高速変形時の流動応力)の向上に有効なTi系析出物及びNb系析出物を生成するために必要な元素でもある。ここで、本明細書において「Ti系析出物及びNb系析出物」とは、Ti及びNbの炭化物、窒化物の他、リン化物(FeTiP、FeNbP)、硫化物(TiS、Ti4C2S2)のことを意味する。フェライト系ステンレス鋼材中に所定量のTi系析出物及びNb系析出物を生成させるためには、Ti含有量を0.01%以上及びNb含有量を0.01%以上とする。ただし、Ti及びNbの過度な添加は、Ti系析出物及びNb系析出物が粗大化し過ぎて靭性の低下をもたらす。そのため、Ti含有量の上限を0.50%、Nb含有量の上限を0.60%とする。また、加工性、製造性及びコストの観点から、Ti含有量及びNb含有量はいずれも0.05~0.30%以下が好ましい。さらに、製造コストの観点から、Ti含有量及びNb含有量はいずれも0.05~0.20%がより好ましい。
Niは、高強度化に寄与し、高速変形時の衝撃吸収特性(高速変形時の流動応力)の向上に有効な元素であり、必要に応じて0.01%以上添加される。ただし、Niの過度な添加は、高温剛性(高温ヤング率)の低下、成分コストの増加、オーステナイト相やマルテンサイト相の生成をもたらして成形性を低下させるため、Ni含有量の上限を2.00%とする。また、靭性及び耐食性を考慮すると、Ni含有量は0.10~1.00%が好ましい。さらに、耐熱性を考慮すると、Ni含有量は0.20~0.50%がより好ましい。
Alは、脱酸元素として添加される元素である。この効果を効率的に発現させるために、必要に応じて0.001%以上添加される。また、Alは、窒化物の形成による加工性の向上、固溶強化による高強度化、耐酸化性の向上にも有効な元素である。ただし、Alの過度な添加は、高温剛性の低下、表面疵の発生、溶接性の低下、及び粗大なAlNによる延性の低下に繋がる。そのため、Al含有量の上限を1.000%とする。また、脱酸効率及び靭性を考慮すると、Al含有量は0.020~0.500%が好ましい。さらに、溶接性を考慮すると、Al含有量は0.020~0.100%未満がより好ましい。
Cuは、耐食性の向上、ε-Cuの析出による高温剛性及び高温強度の向上に寄与するため、必要に応じて0.01%以上添加される。ただし、Cuの含有量が多すぎると延性が著しく低下するため、Cu含有量の上限を2.00%とする。また、耐酸化性及び成分コストを考慮すると、Cu含有量は0.05~1.50%が好ましい。さらに、靭性及び溶接性を考慮すると、Cu含有量は0.10~0.50%がより好ましい。
Moは、耐食性を向上させる元素である。また、Moは、固溶強化元素であり、高速変形時の衝撃吸収特性(高速変形時の流動応力)の向上に有効である。そのため、Moは、必要に応じて0.01%以上添加される。ただし、Moの過度な添加は加工性の低下及びコスト増になる他、靭性が著しく低下するため、Mo含有量の上限を3.00%とする。また、高温剛性及び耐酸化性の観点から、Mo含有量は0.10~1.50%が好ましい。さらに、コスト低減の観点から、Mo含有量は0.10~1.20%がより好ましい。
V及びZrは、Ti及びNbと同様にC及びNと結合し、粗大なCr炭窒化物が生成されるのを抑制する元素である。また、V及びZrは、高速変形時の衝撃吸収特性(高速変形時の流動応力)を向上させるための微細析出物(Zr(C,N)、V(C,N))の生成にも有効な元素である。そのため、V及びZrはそれぞれ、必要に応じて0.01%以上添加される。ただし、V及びZrの過度な添加は、靭性の低下及び高温剛性の低下をもたらすため、V含有量及びZr含有量の上限をいずれも0.50%とする。また、成形性の観点から、V含有量及びZr含有量はいずれも0.05~0.30%が好ましい。さらに、溶接部の高速変形時の衝撃吸収特性や曲げ性を考慮すると、V含有量及びZr含有量はいずれも0.1~0.2%がより好ましい。
Bは、高強度化に有効な元素である他、2次加工割れを抑制する元素である。また、Bは、ホウ化物を形成し、高速変形時の衝撃吸収特性(高速変形時の流動応力)の向上に有効な場合もある。そのため、Bは、必要に応じて0.0002%以上添加される。ただし、Bの過剰な添加は、ボイド形成の起点となり、成形性及び靭性が低下するため、B含有量の上限を0.0050%とする。また、耐食性を考慮すると、B含有量は0.0002~0.0020%が好ましい。さらに、溶接性を考慮すると、B含有量は0.0005~0.0010%がより好ましい。
Caは、Sを固定し熱間加工性を向上させるために、必要に応じて0.0005%以上添加される。一方、ただし、Caの過剰な添加は、耐食性を低下させる他、粗大なCaSによる高速変形時の延性が低下する。そのため、Ca含有量の上限を0.0100%とする。また、製造性の観点から、Ca含有量は0.0005~0.0010%が好ましい。
Wは、耐食性を向上させる元素であり、また固溶強化元素でもある。そのため、使用環境による耐食性レベルに応じて0.10%以上添加される。ただし、Wの過度な添加は、加工性及び靭性の低下、コスト増に繋がるため、W含有量の上限を3.00%とする。W含有量は、0.10~1.50%が好ましい。
Snは、耐食性と高温強度の向上に寄与するため、必要に応じて0.01%以上添加される。ただし、Snの過度な添加は、製造時のスラブ割れが生じる場合がある他、加工時(例えば、穴拡げ時)の粒界割れが顕著になる。そのため、Sn含有量の上限を0.50%とする。さらに、精錬コスト及び製造性を考慮すると、Sn含有量は0.01~0.30%が好ましい。
Coは、高温強度の向上に寄与するため、必要に応じて0.03%以上添加される。ただし、Coの過度な添加は、製造時の靭性低下、コスト増、及び加工性(例えば、穴拡げ性の低下)に繋がる。そのため、Co含有量の上限を0.30%とする。さらに、精錬コスト及び製造性を考慮すると、Co含有量は0.03~0.10%が好ましい。
Mgは、脱酸元素として添加される元素である。また、Mgは、フェライト粒の微細化による製造性の向上、リジングと呼ばれる表面欠陥の改善、溶接部の加工性向上に寄与する。これらの効果を得るために、Mg含有量を0.0002%以上とする。ただし、Mgの過度な添加は、耐食性を著しく低下させる他、粗大なMgOによって加工性(例えば、穴拡げ性)も低下する。そのため、Mg含有量の上限を0.0100%とする。製造性を考慮すると、Mg含有量は0.0002~0.0020%が好ましい。
Sbは、粒界に偏析して高温強度を上げる作用を有する元素である。このSbによる添加効果を得るため、Sb含有量を0.005%以上とする。ただし、Sbの過度な添加は、Sbの偏析により、加工時(例えば、穴拡げ時)の粒界割れ及び溶接時の割れを生じる恐れがあるため、Sb含有量の上限を0.300%とする。高温特性、製造コスト及び靭性を考慮すると、Sb含有量は0.030~0.200%が好ましく、0.050~0.100%がより好ましい。
REM(希土類元素)は、耐酸化性の向上に有効であり、必要に応じて0.002%以上で添加される。ただし、REMの過度に添加してもその効果は飽和し、REMの粒化物による耐食性や穴拡げ性の低下を生じるため、REM含有量の上限を0.200%とする。加工性や製造コストを考慮すると、REM含有量は0.002~0.100%が好ましい。
なお、REMは、一般的な定義に従う。すなわち、REMは、スカンジウム(Sc)、イットリウム(Y)の2元素と、ランタン(La)からルテチウム(Lu)までの15元素(ランタノイド)の総称を指す。REMは、単独で添加しても良いし、混合物であってもよい。
Gaは、耐食性向上や水素脆化抑制のために必要に応じて添加される元素である。特に、これらの効果を得るのに有効な硫化物や水素化物の形成の観点から、Ga含有量の下限を0.0002%とする。また、製造性及びコストの観点から、Ga含有量は0.0020%以上が好ましい。ただし、Gaの過度な添加は、粗大硫化物が生成して加工性(例えば、穴拡げ性)が低下する原因となるため、Ga含有量の上限を0.3000%とする。
Ta及びHfは、高温強度向上に有効な元素であり、必要に応じて添加される。このような効果を得るために、Ta含有量及びHf含有量はいずれも0.001~1.000%とする。高温強度向上の観点から、Ta含有量及びHf含有量は、0.100%以下が好ましく、0.010%以下がより好ましい。
Biは、切削性向上に有効な元素であり、必要に応じて添加される。このような効果を得るために、Bi含有量は0.001~0.020%とする。切削性向上の観点から、Bi含有量は、0.015%以下が好ましい。
Ti系析出物及び/又はNb系析出物の粒径は、フェライト系ステンレス鋼材の断面を走査型電子顕微鏡で観察することによって測定することができる。また、Ti系析出物及び/又はNb系析出物の粒径は、面積同等の円相当径として求める。
ここで、103/秒の歪速度で引張試験を行った際の10%歪における流動応力は、衝突事故などによる衝撃を想定した高速変形時の衝撃吸収特性を表す指標である。この流動応力が500MPa以上であれば、高速変形時の衝撃吸収特性に優れており、一般的な自動車の電池部品の衝突安全性が確保できるレベルであるということができる。フェライト系ステンレス鋼材から構成される電池部品の厚みの低減による軽量化を考慮すると、この流動応力は、550MPa以上がより好ましく、600MPa以上が更に好ましい。
図1に示されるように、発明例は、10%歪の流動応力が500MPa以上と高く、高速変形時の衝撃吸収特性に優れるのに対し、比較例は、10%歪の流動応力が500MPa未満である。これは、衝突事故のような歪速度が103/秒と極めて高い場合に、Ti系析出物及び/又はNb系析出物の存在が、転位の移動の妨げに有効に作用し、流動応力の増加に繋がることを示している。
ここで、900℃におけるヤング率は、高温剛性を表す指標である。衝突事故などが起こった場合、破壊された電池の内部が瞬間的に900℃程度の高温に達するため、他の電池を構成する電池部品も高温に曝される。このとき、900℃におけるヤング率が80GPa未満であると、電池部品が変形し、熱暴走に発展し易くなる。これに対して900℃におけるヤング率が80GPa以上であれば、電池部品の変形を抑制し、熱暴走を抑制することができる。フェライト系ステンレス鋼材から構成される電池部品の厚みの低減による軽量化を考慮すると、900℃におけるヤング率は、90GPa以上がより好ましい。なお、900℃におけるヤング率は、高いほど高温剛性に優れるといえるため、その上限は特に限定されないが、例えば200GPa、一般的に150GPaである。
900℃におけるヤング率は、JIS Z2280:1993に規定される方法に準拠し、共振法によって求めることができる。
ここで、常温における破断伸びは、加工性を表す指標である。常温における破断伸びを30%以上とすることにより、様々な形状を有する電池部品への加工性が担保される。常温における破断伸びの上限は、特に限定されないが、例えば50%である。
常温における破断伸びは、フェライト系ステンレス鋼材の圧延方向が平行部と平行になるように採取したJIS13号B試験片を用い、JIS Z2241:2011に準拠し、引張試験を行うことによって求めることができる。
ここで、最大孔食深さは、耐食性を表す指標である。最大孔食深さを200μm未満とすることにより、耐食性に優れるということができる。
最大孔食深さは、フェライト系ステンレス鋼材に対して、JASO-CCT試験を30サイクル行って錆落とし処理を施し、次いで顕微鏡を用いた焦点深度法で測定することによって求めることができる。
本発明の実施形態に係るフェライト系ステンレス鋼材の製造方法は、上記の特徴を有するフェライト系ステンレス鋼材を製造可能な方法であれば特に限定されない。
例えば、本発明の実施形態に係るフェライト系ステンレス鋼材の製造方法は、上記の組成を有する冷延材を、850~1050℃で焼鈍した後、800℃までの冷却速度を10℃/秒以下として冷却することにより行われる。このような条件に制御することにより、上記の特徴を有するフェライト系ステンレス鋼材を製造することができる。なお、上記のようにして焼鈍及び冷却した後、必要に応じて酸洗処理を行ってもよい。
以下、上記の製造方法の詳細について説明する。
本発明の実施形態に係る電池部品は、上記のフェライト系ステンレス鋼材を備える。上記のフェライト系ステンレス鋼材は、高速変形時の衝撃吸収特性及び高温剛性に優れているため、この電池部品は、衝突事故などによって電池に衝撃が加えられた際に、電池の保護性能及び熱暴走に対する耐性に優れている。
電池部品としては、特に限定されないが、例えば、電池ケース、電池パック、電池モジュール、電池カバーなどが挙げられる。
以下の手順に従ってフェライト系ステンレス鋼板を作製した。
表1及び2に示す組成を有するステンレス鋼を溶製し、熱間圧延して厚み3.8mmの熱延板を得た後、酸洗することによって熱延酸洗板を得た。次に、熱延酸洗板を冷間圧延して厚み0.6mmの冷延板を得た。次に、冷延板を表3及び4に示す条件で焼鈍及び冷却した後、酸洗を施し、冷延焼鈍板(フェライト系ステンレス鋼板)を得た。
JIS G0555:2003に規定される点算法に従い、冷延焼鈍板の断面を顕微鏡観察し、組織全体に占める析出物の存在領域の面積比率から析出物の量を求めた。具体的には、冷延焼鈍板の圧延方向に平行な厚み方向断面が観察面となるように樹脂埋めを施し、鏡面研磨を行った後、光学顕微鏡を用いて400倍の倍率で厚みの1/4~3/4における介在物を観察した。このとき、測定レンズに20×20の格子を付けた光学顕微鏡を用いて、60視野観察し、格子にかかる介在物をカウントして面積比率を算出し、これを析出物の量(体積%)とした。
析出物の粒径は、冷延焼鈍板の圧延方向に平行な厚み方向断面が観察面となるように樹脂埋めを施し、鏡面研磨を行った後、走査型電子顕微鏡を用いて3000倍の倍率で厚みの1/4~3/4における析出物を観察した。観察は10視野で行い、最大の析出物の面積を算出し、円相当径を求めて析出物の粒径とした。なお、析出物は、走査型電子顕微鏡付属のEDS分析を行い、析出物のTi及び/又はNbの含有量が母材の含有量以上となる場合に、析出物と判断した。
冷延焼鈍板から平行部幅2.0mm、標線距離4.8mmの引張試験片を引張方向が圧延方向になるように採取し、高速引張試験を行った。高速引張試験は、高速引張試験機(株式会社鷺宮製作所製の検力ブロック式高速引張試験機)を用い、歪速度を103/秒として行い、流動応力と歪との関係を求めた。そして10%の歪における流動応力を求めた。
900℃におけるヤング率は、JIS Z2280:1993に規定される方法に準拠し、共振法によって求めた。具体的には、冷延焼鈍板から圧延方向長さ60mm、幅方向10mmの測定用試験片を採取し、弾性率測定装置(日本テクノプラス株式会社製のEG-HT弾性率測定装置)を用い、900℃で共振法によって測定した。
冷延焼鈍板から圧延方向が平行部と平行になるように採取したJIS13号B試験片を用い、JIS Z2241:2011に準拠し、引張試験機(株式会社島津製作所製の精密万能試験機オートグラフAG-X)を用い、常温(25℃)にて引張試験を行うことによって求めた。
冷延焼鈍板から圧延方向長さ150mm、幅方向75mmの測定用試験片を採取した。次に、JASO-CCT試験(M609-91の条件に従い、塩水噴霧(35℃、濃度5%、2時間)、乾燥(60℃、25%RH、4時間)、湿潤(50℃、95%RH、2時間)を1サイクルとする)を30サイクル行った後、錆落とし処理を施した。次に、顕微鏡を用い、焦点深度法によって最大孔食深さを測定した。この評価において、最大孔食深さが200μm未満であったものを○、最大孔食深さが200μm以上を×とした。
一方、表6に示されているように、比較例1~4の冷延焼鈍板は、焼鈍温度又は冷却速度の条件が適切でなく、析出物の量が少なすぎたため、103/秒の歪速度で引張試験を行った際の10%歪における流動応力、及び900℃におけるヤング率のどちらか一方又は両方が低くなった。また、比較例5~31の冷延焼鈍板は、所定の組成を満たしていないとともに、一部の比較例では焼鈍温度も適切でなかったため、103/秒の歪速度で引張試験を行った際の10%歪における流動応力、及び900℃におけるヤング率のどちらか一方又は両方が低くなった。さらに、比較例3~31の冷延焼鈍板は、常温における破断伸び及び耐食性(最大孔食深さ)のどちらか一方又は両方の結果も十分でなかった。
Ti系析出物及び/又はNb系析出物を0.010体積%以上含む、電池部品用フェライト系ステンレス鋼材。
900℃におけるヤング率が80GPa以上である、[1]~[3]のいずれか1つに記載の電池部品用フェライト系ステンレス鋼材。
(1)常温における破断伸びが30%以上である
(2)最大孔食深さが200μm未満である
の1つ以上を満たす、[1]~[4]のいずれか1つに記載の電池部品用フェライト系ステンレス鋼材。
Claims (11)
- 質量基準で、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%を含有し、Ti:0.01~0.50%及びNb:0.01~0.60%から選択される1種又は2種を更に含有し、残部がFe及び不純物からなる組成を有し、
Ti系析出物及び/又はNb系析出物を0.010体積%以上含む、電池部品用フェライト系ステンレス鋼材。 - 質量基準で、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:0.03~0.30%、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%から選択される1種又は2種以上を更に含有する、請求項1に記載の電池部品用フェライト系ステンレス鋼材。
- 前記Ti系析出物及び/又は前記Nb系析出物の粒径が10μm以下である、請求項1又は2に記載の電池部品用フェライト系ステンレス鋼材。
- 103/秒の歪速度で引張試験を行った際の10%歪における流動応力が500MPa以上であり、且つ
900℃におけるヤング率が80GPa以上である、請求項1~3のいずれか一項に記載の電池部品用フェライト系ステンレス鋼材。 - 以下の特性:
(1)常温における破断伸びが30%以上である
(2)最大孔食深さが200μm未満である
の1つ以上を満たす、請求項1~4のいずれか一項に記載の電池部品用フェライト系ステンレス鋼材。 - 厚みが1.0mm以下である、請求項1~5のいずれか一項に記載の電池部品用フェライト系ステンレス鋼材。
- 質量基準で、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%を含有し、Ti:0.01~0.50%及びNb:0.01~0.60%から選択される1種又は2種を更に含有し、残部がFe及び不純物からなる組成を有する冷延材を、850~1050℃で焼鈍した後、800℃までの冷却速度を10℃/秒以下として冷却する、電池部品用フェライト系ステンレス鋼材の製造方法。
- 前記冷延材は、質量基準で、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:0.03~0.30%、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%から選択される1種又は2種以上を更に含有する、請求項7に記載の電池部品用フェライト系ステンレス鋼材の製造方法。
- 前記冷却は、800℃から400℃までの冷却速度を10℃/秒超とする、請求項7又は8に記載の電池部品用フェライト系ステンレス鋼材の製造方法。
- 800℃から400℃までの前記冷却速度が12℃/秒以上である、請求項9に記載の電池部品用フェライト系ステンレス鋼材の製造方法。
- 請求項1~6のいずれか一項に記載の電池部品用フェライト系ステンレス鋼材を備える電池部品。
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| CN202380062299.0A CN119895064A (zh) | 2022-09-26 | 2023-08-31 | 电池部件用铁素体系不锈钢材及其制造方法以及电池部件 |
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