CN109072449B - Steel plate for outer can of battery, outer can of battery and battery - Google Patents
Steel plate for outer can of battery, outer can of battery and battery Download PDFInfo
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- CN109072449B CN109072449B CN201780027816.5A CN201780027816A CN109072449B CN 109072449 B CN109072449 B CN 109072449B CN 201780027816 A CN201780027816 A CN 201780027816A CN 109072449 B CN109072449 B CN 109072449B
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 130
- 239000010959 steel Substances 0.000 title claims abstract description 130
- 239000010410 layer Substances 0.000 claims abstract description 111
- 238000009792 diffusion process Methods 0.000 claims abstract description 91
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000002344 surface layer Substances 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000007747 plating Methods 0.000 abstract description 39
- 230000007797 corrosion Effects 0.000 abstract description 24
- 238000005260 corrosion Methods 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 21
- 229910000760 Hardened steel Inorganic materials 0.000 abstract description 11
- 239000000463 material Substances 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 238000000465 moulding Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000000137 annealing Methods 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 238000005097 cold rolling Methods 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/20—Deep-drawing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention provides a steel plate for a battery outer can, a battery outer can and a battery using the steel plate for the battery outer can, wherein the steel plate for the battery outer can is used in a post-plating method, can inhibit scratch generation even if a forming die made of hardened steel is used for repeatedly stamping forming, and the obtained battery outer can has excellent corrosion resistance. The steel sheet for a can for a battery outer can has Fe-Ni diffusion layers on the surface layers on both sides of the steel sheet, and the Fe-Ni diffusion layers are attached to each side of the steel sheet in an amount of 50mg/m in terms of Ni conversion 2 ～500mg/m 2 。
Description
Technical Field
The invention relates to a steel plate for a battery outer can, a battery outer can and a battery.
Background
As the battery, for example, a primary battery such as an alkaline manganese battery, a secondary battery such as a lithium ion battery mounted on a notebook computer or a hybrid car, and the like are known.
From the viewpoint of corrosion resistance, ni plating is performed on the surface of a steel plate constituting an outer can (battery outer can) used for these batteries to form a Ni layer.
There are 2 manufacturing methods for the outer can of the battery according to the difference in the steps of performing Ni plating.
One is a plating method in which a Ni-plated steel sheet is press-formed into a battery outer can, and then plating is not performed. The other is a post-plating method in which Ni plating is performed on the surface of the battery outer can after press forming by a barrel plating method or the like.
As a steel sheet for a battery outer can used in the post-plating method, for example, patent document 1 discloses "a Ni-plated steel sheet for a container characterized in that a fe—ni diffusion layer having a thickness of 0.5 μm to 4 μm is provided on a surface to be an inner surface of the container by press forming, a Ni layer having a thickness of 0.25 μm to 4 μm is further provided thereon, and an adhesion amount of 0.05g/m is provided on a surface to be an outer surface of the container 2 Above and less than 1.5g/m 2 The Ni diffuses inward, and the mass ratio of Ni/(Fe+Ni) in the surface layer is 0.1 to 0.9 "(claim 1).
In patent document 1, such a steel sheet for a battery can (container Ni-plated steel sheet) is press-formed to form a battery can, and then Ni plating is performed on the outer surface thereof by a method such as barrel plating.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 4995140
Disclosure of Invention
As a material of a forming die (mold) used for press forming by the post-plating method, cemented carbide is often used, and a relatively brittle hardened steel may be used.
When press forming of the steel sheet for a battery outer can (container Ni-plated steel sheet) of patent document 1 is repeated using a forming die made of hardened steel, the forming die is gradually scratched, and as a result, there is a possibility that the formed steel sheet for a battery outer can may be scratched. In such a case, the obtained battery can may have a risk of deterioration in corrosion resistance due to scratch.
Accordingly, an object of the present invention is to provide a steel sheet for a can, which is used in a post-plating method, can suppress the occurrence of scratches even when press forming is repeatedly performed using a forming die made of hardened steel, and has excellent corrosion resistance, and a can for a can and a battery using the same.
The present inventors have intensively studied and found that the above object can be achieved by using a steel sheet for a battery outer can having a specific fe—ni diffusion layer on the surface layers on both surfaces of the steel sheet, and completed the present invention.
That is, the present invention provides the following [1] to [8].
[1]A steel sheet for a can for a battery outer can, comprising Fe-Ni diffusion layers on both surfaces of the steel sheet, wherein the Fe-Ni diffusion layers are adhered to each surface of the steel sheet in an amount of 50mg/m in terms of Ni conversion 2 ～500mg/m 2 。
[2] The steel sheet for a battery outer can according to item [1], wherein the Ni ratio of the outermost surface of the Fe-Ni diffusion layer is 1.0% or more and less than 20.0%. Wherein the Ni ratio is a ratio of the Ni amount at the outermost surface of the Fe-Ni diffusion layer to a total amount of the Fe amount and the Ni amount, and the Fe amount and the Ni amount are in atomic%.
[3] The steel sheet for a can for a battery outer tube as described in the above [1] or [2], wherein the Fe-Ni diffusion layer has a thickness of 0.01 μm or more and less than 0.5 μm.
[4]A can for a battery can, comprising a steel plate having a can shape and Fe-Ni diffusion layers on the inner and outer surfaces thereof, wherein the Fe-Ni diffusion layers on the outer surface side of the steel plate further comprise Ni layers, and wherein a part of the Fe-Ni diffusion layers on the outer surface side of the steel plate is 50mg/m in terms of Ni conversion on each surface of the steel plate 2 ～500mg/m 2 The Fe-Ni diffusion layer A of (C).
[5] The battery outer can according to item [4], wherein the Ni ratio of the outermost surface of the Fe-Ni diffusion layer A is 1.0% or more and less than 20.0%. The Ni ratio is a ratio of the Ni amount at the outermost surface of the Fe-Ni diffusion layer to a total amount of the Fe amount and the Ni amount, and the unit of the Fe amount and the Ni amount is atomic%.
[6] The battery outer can according to the item [4] or [5], wherein the Fe-Ni diffusion layer A has a thickness of 0.01 μm or more and less than 0.5 μm.
[7] The battery outer can according to any one of [4] to [6], wherein the Ni layer has a thickness of 1 μm or more.
[8] A battery comprising the can of any one of [4] to [7], an electrolyte disposed in the can, an electrode, and a separator.
According to the present invention, it is possible to provide a steel sheet for a can, which is used in a post-plating method, can suppress the occurrence of scratches even when press forming is repeatedly performed using a forming die made of hardened steel, and can provide a can for a can and a battery using the same, and the obtained can for a can has excellent corrosion resistance.
Detailed Description
[ Steel plate for Battery outer can ]
The steel sheet for a can for a battery outer can of the present invention (hereinafter also simply referred to as "steel sheet for a can of the present invention") has Fe-Ni diffusion layers on both surfaces of the steel sheet, and the Fe-Ni diffusion layers have an adhesion amount in terms of Ni (hereinafter also referred to as "Ni adhesion amount") of 50mg/m on each surface of the steel sheet 2 ～500mg/m 2 。
The steel sheet for a can of the present invention is a steel sheet for a can of a battery outer can used in a post-plating method, can suppress occurrence of scratches even when press forming is repeatedly performed using a forming die made of hardened steel, and the obtained can of a battery outer can has excellent corrosion resistance.
The reason for this is presumed to be as follows.
First, the steel sheet for a battery outer can used in the post-plating method described in patent document 1 has "an fe—ni diffusion layer having a thickness of 0.5 μm or more and … … on a surface to be an inner surface of a container by press forming". The Ni adhesion amount of the Fe-Ni diffusion layer was 4500mg/m as a result of conversion 2 The above.
In the steel sheet for a battery outer can of patent document 1, the Ni adhering amount of the fe—ni diffusion layer is excessive, and the steel sheet is hardened, and a forming die made of brittle hardened steel is gradually scratched during repeated press forming. Further, the use of a damaged forming die causes scratches on the formed steel sheet for the battery outer can.
However, the Fe-Ni diffusion layer of the steel sheet for cans of the present invention has a Ni adhesion amount moderately low to 500mg/m 2 Hereinafter, it is softened to such an extent that it does not scratch the molding die made of hardened steel. Therefore, the formed steel sheet for the battery outer can be suppressed from being scratched (hereinafter also referred to as "excellent in scratch resistance"). Further, the steel sheet for cans of the present invention is excellent in scratch resistance, and thus the obtained outer can for a battery is also excellent in corrosion resistance.
When the amount of Ni attached to the fe—ni diffusion layer of the steel sheet for a can of the present invention is too small, the corrosion resistance of the obtained outer can for a battery may be deteriorated. However, the steel sheet for cans of the present invention has a Ni adhesion amount of the Fe-Ni diffusion layer moderately high to 50mg/m 2 As described above, the corrosion resistance (hereinafter also simply referred to as "corrosion resistance") when the outer can is manufactured is excellent.
More specifically, when the outer can is manufactured, the electrochemical stability of the fe—ni diffusion layer is good on the inner surface thereof, and the corrosion resistance to the content is improved as compared with the case where the fe—ni diffusion layer is not present or the case where the fe—ni diffusion layer is too small.
On the other hand, although Ni plating is performed on the outer surface of the steel sheet by barrel plating or the like after molding, a plurality of pinholes exist in the Ni layer, and corrosion progresses from there. However, the base layer of the Ni layer is appropriately provided with the Fe-Ni diffusion layer, and the potential difference between the Ni layer and the underlayer can be reduced as compared with the case where the Fe-Ni diffusion layer is not present or is excessively small, thereby improving the corrosion resistance.
Hereinafter, each part of the steel sheet for cans of the present invention will be described in more detail.
< Steel sheet >
The type of the steel sheet is not particularly limited. A steel plate (e.g., a low-carbon steel plate or an extremely low-carbon steel plate) that is generally used as a battery container material may be employed. However, the inclusion of Cr in the steel sheet may cause the steel to harden and reduce formability, or Cr oxide may be formed on the surface of the steel sheet during annealing, and thus a desired surface state may not be obtained. Therefore, the Cr content of the steel sheet is preferably less than 3 mass%, more preferably less than 1 mass%.
The method for producing the steel sheet is not particularly limited either. For example, the steel sheet can be produced from a usual steel sheet production step by hot rolling, pickling, cold rolling, annealing, temper rolling, and the like.
In the present invention, since the formation of the fe—ni diffusion layer is necessary, ni plating is performed on the unannealed steel sheet after cold rolling, and it is most efficient in terms of production to diffuse Ni plating into the inside of the steel sheet while annealing the steel sheet. Therefore, as the steel sheet, an unannealed steel sheet after cold rolling is preferably used.
< Fe-Ni diffusion layer >
The steel sheet for cans of the present invention has Fe-Ni diffusion layers on the surface layers on both sides of the steel sheet.
Ni adhesion amount
The Fe-Ni diffusion layer was deposited on each surface of the steel sheet in terms of Ni in an amount (Ni deposited amount) of 50mg/m 2 ～500mg/m 2 . As described above, the steel sheet for cans of the present invention is excellent in both scratch resistance and corrosion resistance. For the reason of more excellent scratch resistance, the Ni adhesion amount of the Fe-Ni diffusion layer is preferably 350mg/m 2 Hereinafter, 300mg/m is more preferable 2 The following is given.
The Ni adhesion amount of the Fe-Ni diffusion layer can be measured by performing surface analysis by fluorescence X-ray analysis. At this time, a calibration curve concerning the Ni adhering amount is determined in advance using a Ni adhering sample having a known Ni adhering amount, and the relative Ni adhering amount is obtained using the calibration curve. The fluorescent X-ray analysis is performed, for example, under the following conditions.
Device: fluorescent X-ray analyzer System3270 manufactured by Physics corporation
Diameter measurement: 30mm
Measuring atmosphere: vacuum
Spectrum: ni-K alpha
Slit: COARSE
Spectroscopic crystal: TAP (TAP)
Peak count of Ni-kα by fluorescent X-ray analysis of the Fe-Ni diffusion layer measured under the above conditions. Using a standard sample whose adhesion amount is known by measuring the adhesion amount by a gravimetric method, a calibration curve concerning the Ni adhesion amount was obtained in advance, and the relative Ni adhesion amount was obtained from the calibration curve.
Thickness (thickness)
In the steel sheet for cans of the present invention, the thickness of the Fe-Ni diffusion layer is preferably 0.01 μm or more and less than 0.5 μm for the reason that the Fe-Ni diffusion layer is easily maintained after molding and the scratch resistance and corrosion resistance are more excellent, more preferably 0.4 μm or less and still more preferably 0.38 μm or less for the reason that the scratch resistance is more excellent.
The thickness of the Fe-Ni diffusion layer can be measured by GDS (glow discharge emission analysis). Specifically, first, sputtering was performed from the surface of the Fe-Ni diffusion layer toward the inside of the steel sheet, and analysis was performed in the depth direction, and the sputtering time was obtained at which the Ni strength became 1/10 of the maximum value. Next, the relation between the sputtering depth and the sputtering time was obtained by using GDS using pure iron. By using this relation, the sputtering depth was calculated by pure iron conversion from the sputtering time of 1/10 of the previously obtained Ni intensity as the maximum value, and the calculated value was used as the thickness of the fe—ni diffusion layer. GDS was performed under the following conditions.
Device: GDA750 manufactured by Physics Co., ltd
Anode inside diameter: 4mm of
Analysis mode: high frequency low voltage mode
Discharge power: 40W
Control pressure: 2.9hPa
Detector: photomultiplier tube
Detection wavelength: ni= 341.4nm
Ni ratio
In the steel sheet for cans of the present invention, the Ni ratio at the outermost surface of the fe—ni diffusion layer (hereinafter also simply referred to as "Ni ratio") is preferably 1.0% or more and less than 20.0% for the reason that scratch resistance and corrosion resistance are more excellent.
The reason why the Ni ratio of the outermost surface of the fe—ni diffusion layer is important is that although Ni of the outermost surface of the fe—ni diffusion layer has a direct effect on corrosion resistance, the corrosion resistance improvement effect of Ni diffused into steel is small. On the other hand, when the Ni ratio is too high, the outermost surface becomes hard, and scratch resistance may become insufficient. Therefore, the suitable range of the Ni ratio is 1.0% or more and less than 20.0% as described above.
The lower limit of the Ni ratio is more preferably 3.0% for the reason that scratch resistance is more excellent. For the same reason, the upper limit of the Ni ratio is more preferably 15.0%, and still more preferably 13.0%.
The Ni ratio (unit:%) at the outermost surface of the Fe-Ni diffusion layer is the ratio of the Ni amount to the total amount of the Fe amount and the Ni amount at the outermost surface of the Fe-Ni diffusion layer, i.e., calculated from the formula "Ni amount/(Fe amount+Ni amount) ×100". The unit of the Fe amount and the Ni amount is atomic%.
The Fe content (unit: atomic%) and Ni content (unit: atomic%) on the outermost surface of the Fe-Ni diffusion layer can be measured by ultrasonic cleaning of a steel sheet having the Fe-Ni diffusion layer formed therein in acetone for 10 minutes, and then measuring the resultant steel sheet by Auger electron spectroscopy without sputtering. The auger electron spectroscopy was performed at 10 points in different fields of view in the same sample, and the Fe and Ni amounts were average values obtained by using the measurement results at 10 points, respectively. Auger electron spectroscopy was performed under the following conditions.
Device: PHI660 manufactured by ULVAC-PHI Co
Observation and analysis conditions: acceleration voltage 10.0kV and current value 0.5 mu A
Observation magnification is 1,000 times, measurement range is 540-900 eV
Method for forming Fe-Ni diffusion layer
The method of forming the fe—ni diffusion layer on the surface layers on both sides of the steel sheet is not particularly limited, and the following method is given as an example.
First, after pre-treatment (degreasing, pickling, etc.) is performed as needed on the non-annealed steel sheet after cold rolling, ni plating is performed by appropriately adjusting conditions such as current density using a Ni plating bath. Examples of the Ni plating bath include a watter bath (Watts bath), an sulfamic acid bath, a boron fluoride bath, and a chloride bath.
At this time, the Ni-plated adhesion amount was 50mg/m on each surface of the steel sheet 2 ～500mg/m 2 . Thus, the Ni adhesion amount of the Fe-Ni diffusion layer formed was 50mg/m 2 ～500mg/m 2 。
Next, the steel sheet after Ni plating is annealed (preferably, continuous annealing) for the purpose of recrystallization treatment of the steel sheet. Thus, as the steel sheet is annealed, the Ni-plated steel sheet is diffused into the steel sheet to form an Fe-Ni diffusion layer.
As annealing conditions, a soaking temperature of 600 to 800℃is preferable, and a holding time at the soaking temperature is preferably 10 to 60 seconds. The shorter the holding time at the soaking temperature, the less likely Ni diffuses into the steel, and the higher the Ni ratio at the outermost surface, the more preferably the holding time at the soaking temperature is less than 30 seconds from the viewpoint of corrosion resistance.
The annealing condition is preferable because the thickness of the Fe-Ni diffusion layer to be formed can be 0.01 μm or more and less than 0.5 μm, and the Ni ratio at the outermost surface can be 1.0% or more and less than 20.0%.
After the formation of the fe—ni diffusion layer, shape correction, surface roughness adjustment, and the like may be performed by performing temper rolling, as necessary.
[ method for manufacturing Battery outer can ]
Next, a method for manufacturing a battery outer can using the can steel sheet of the present invention (hereinafter, also referred to as "the manufacturing method of the present invention" for convenience) will be described.
The production method of the present invention includes, for example, a method comprising the steps of: a step of forming the steel sheet for a can of the present invention into a can shape (for example, cylindrical shape) of a battery outer can by press forming using a forming die; and then, ni plating is performed on the outer surface of the steel sheet for can of the present invention molded into the shape of the can of the outer can of the battery to form a Ni layer.
< Forming (stamping Forming) >
The method of molding (press molding) is not particularly limited, and can be carried out by a general method used for molding the battery outer can. For example, the steel sheet for cans of the present invention is die-cut into a round shape, drawn into a cup shape, and then formed into a cylindrical shape or the like through redrawing and DI (drawing and ironing ) steps.
In this case, a cemented carbide is often used as a material of the molding die, but a relatively brittle hardened steel may be used. As described above, it is considered that the fe—ni diffusion layer of the steel sheet for can of the present invention does not scratch the forming die made of hardened steel, and therefore the scratch of the formed steel sheet for can of outer can of battery can is suppressed.
The Ni adhering amount, thickness and Ni ratio of the fe—ni diffusion layer that has been subjected to press forming cannot be changed while maintaining the state before press forming.
However, in the steel sheet for a can of the present invention, at least a part of the portion that is the outer surface side of the outer can (for example, the portion that is the end surface of the protrusion on the positive electrode side of the outer can) is not press-formed and is maintained in a non-processed state.
Therefore, at least a part of the outer surface side of the can for a battery (can for a battery of the present invention) obtained using the steel sheet for a can of the present invention maintains the Ni adhesion amount, thickness, and Ni ratio of the fe—ni diffusion layer of the steel sheet for a can of the present invention before press forming as it is.
< Ni plating after Forming into Can shape of Battery outer can >
The method for plating Ni is not particularly limited, and conventionally known methods can be employed. For example, the steel sheet for cans of the present invention molded into the shape of a can for a battery can is subjected to Ni plating by barrel plating using a Ni plating bath under conditions such as current density suitably adjusted. Examples of the Ni plating bath include a watt bath, an sulfamic acid bath, a boron fluoride bath, and a chloride bath.
Thus, ni plating is performed on the Fe-Ni diffusion layer on at least the outer surface side of the can steel sheet of the present invention molded into the shape of a can for a battery outer can to form a Ni layer.
In this case, since the steel sheet for can of the present invention is molded into the shape of the can of the outer can of the battery, ni plating is not likely to intrude into the inside thereof, and thus Ni plating is not likely to be performed on the inner surface of the steel sheet for can of the present invention in the shape of the can of the outer can of the battery. Of course, the inner surface of the can steel sheet of the present invention in the shape of a can of a battery outer can may be plated with Ni to form a Ni layer in the same manner as the outer surface.
The thickness of the Ni-plated layer (Ni layer) formed on the Fe-Ni diffusion layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of corrosion resistance. The upper limit of the thickness of the Ni layer is not particularly limited, and is preferably 7 μm or less from the viewpoint of economy, for example.
[ Battery outer can ]
The outer can of the present invention is a can obtained by using the steel sheet for can of the present invention.
More specifically, the battery can of the present invention has Fe-Ni diffusion layers on the inner and outer surfaces of a steel plate in the shape of a battery can, and further has a Ni layer on the Fe-Ni diffusion layer on the outer surface side of the steel plate, wherein a part of the Fe-Ni diffusion layer on the outer surface side of the steel plate is an adhesion amount in terms of Ni conversion of 50mg/m on each surface of the steel plate 2 ～500mg/m 2 The Fe-Ni diffusion layer A of (C).
The outer can of the present invention is first formed by press forming a steel plate into the outer can shape, and fe—ni diffusion layers are formed on the surface layers of both surfaces (inner surface and outer surface) of the steel plate in the same manner as the steel plate for a can of the present invention. Then, ni plating is performed on at least the Fe-Ni diffusion layer on the outer surface side of the steel sheet to form a Ni layer.
As described above, the Fe-Ni diffusion layer of at least a part of the outer surface side of the can of the present invention maintains the Fe-Ni diffusion layer (Ni adhering amount: 50 mg/m) of the steel sheet for can of the present invention before press molding as it is 2 ～500mg/m 2 )。
That is, in the can of the present invention, at least a part of the Fe-Ni diffusion layer on the outer surface side of the can-shaped steel plate is Ni-attached in an amount of 50mg/m 2 ～500mg/m 2 The Fe-Ni diffusion layer A of (C).
The suitable ranges of the Ni adhesion amount, thickness and Ni ratio of the Fe-Ni diffusion layer a in the outer can of the present invention are the same as those of the Fe-Ni diffusion layer of the steel sheet for a can of the present invention.
In the outer can of the battery of the present invention, the thickness of the Ni layer on the fe—ni diffusion layer is preferably 1 μm or more, more preferably 2 μm or more, as described above. The upper limit is not particularly limited, but is preferably 7 μm or less.
[ Battery ]
The battery of the present invention comprises the battery can of the present invention, and an electrolyte, an electrode, and a separator disposed inside the battery can of the present invention.
That is, the battery of the present invention is such that the inside of the battery can of the present invention is filled with at least the electrolyte, the electrode, and the separator, which are components necessary for the battery, and may be further filled with other components as needed.
The battery of the present invention has excellent corrosion resistance due to the use of the battery can of the present invention.
Examples (example)
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.
< production of Steel sheet for Battery outer can >
As a steel sheet, an unannealed Nb-added extremely low carbon steel (steel component comprising, in mass%, 0.002% of C, 0.02% of Si, 0.15% of Mn, 0.01% of P, 0.008% of S, 0.02% of Ni, and 0.01%) was used in a cold-rolled state having a sheet thickness of 0.25 mm. The steel sheet is subjected to pretreatment including degreasing and pickling.
Ni plating was performed on the pretreated steel sheet using a watt bath. At this time, the Ni-attached amount (unit: mg/m) shown in Table 1 below was used 2 ) The current density and other conditions are appropriately adjusted.
Next, the Ni-plated steel sheet was introduced into a continuous annealing line, the steel sheet was annealed, ni was diffused into the steel sheet, and fe—ni diffusion layers were formed on the surface layers on both surfaces of the steel sheet. In this case, the thickness (unit: μm) and Ni ratio (unit:%) of the Fe-Ni diffusion layer were set to the values shown in Table 1 by using the annealing conditions (soaking temperature and holding time) shown in Table 1.
After forming the Fe-Ni diffusion layer, temper rolling was performed to obtain steel sheets for outer can of battery of test materials No.1 to 27.
< manufacture of Battery outer can >
Molding (shaping)
The obtained battery can was punched out of a steel plate into a round shape, drawn into a cup shape, and then formed into a cylindrical 18650-type battery can shape by re-drawing and DI steps. The thickness of the side wall portion was reduced to 0.15mm by DI step.
Ni plating
Then, ni plating was performed by barrel plating to form a Ni layer having a thickness of 4 μm on at least the outer surface of the steel sheet for the can of the can which was molded into the can shape. Thus, a battery can was obtained.
< evaluation >
Corrosion resistance
An aqueous solution obtained by mixing 5g of sodium chloride and 1.5cc of a 30% aqueous hydrogen peroxide solution in 100g of pure water was prepared. The obtained outer can was immersed in the aqueous solution at room temperature for 16 hours. After the impregnation, the battery outer can was pulled out, whether or not a hole was formed was visually confirmed, the case where a hole was confirmed was designated as "B", and the case where a hole was not confirmed was designated as "a", which are described in table 1 below. "A" means excellent in corrosion resistance.
Scratch resistance
The above-mentioned molding was repeated using a molding die made of hardened steel, and the number of times (number of cans to be produced) until scratches were visually confirmed on the surface of the steel sheet for the outer can of the battery, which had been molded into the outer can shape, was counted.
In table 1 below, the number of cans until scratch was confirmed was 50000 or less, the number of cans exceeding 50000 and being 70000 or less was "C", the number of cans exceeding 70000 and being 100000 or less was "B", and the number of cans exceeding 100000 and no scratch was confirmed yet was "a".
"A", "B" or "C" means excellent scratch resistance. In practice, "a" or "B" is preferable, and "a" is more preferable.
TABLE 1
TABLE 1
As shown in Table 1, the Ni adhesion amount of the Fe-Ni diffusion layer exceeds 500mg/m 2 The test materials No.10 to 11 and 22 to 23 were poor in scratch resistance. The Ni adhesion amount of the Fe-Ni diffusion layer is less than 50mg/m 2 The test materials No.12 and 24 of (C) were poor in corrosion resistance.
In contrast, the Ni adhesion amount of the Fe-Ni diffusion layer was 50mg/m 2 ～500mg/m 2 The test materials No.1 to 9, 13 to 21 and 25 to 27 were excellent in scratch resistance and scratch resistance.
Comparing test materials Nos. 1 to 9, 13 to 21 and 25 to 27, the test materials Nos. 1 to 9, 13 to 21 and 26 to 27 having Ni ratios of 1.0% or more and less than 20.0% at the outermost surface of the Fe-Ni diffusion layer were more excellent in scratch resistance than the test material No.25 having Ni ratios of 20.0% or more.
Test materials No.1 to 9 were compared, and scratch resistance was better for test materials No.1 to 4 and 8 to 9, which had lower Ni ratios than for test materials No.5 to 7.
Similarly, test materials Nos. 13 to 21 were compared, and scratch resistance was better for test materials Nos. 13 to 16 and 20 to 21, which had lower Ni ratios than for test materials Nos. 17 to 19.
Claims (6)
1. A steel sheet for a battery outer can, comprising Fe-Ni diffusion layers on both surfaces of the steel sheet,
the Fe-Ni diffusion layer was adhered to each surface of the steel sheet in an amount of 200mg/m in terms of Ni conversion 2 ～500mg/m 2 ，
The Ni ratio at the outermost surface of the Fe-Ni diffusion layer is 1.0% or more and less than 20.0%,
the Ni ratio is a ratio of the Ni amount at the outermost surface of the Fe-Ni diffusion layer with respect to a total amount of Fe amount and Ni amount in atomic%.
2. The steel sheet for a battery outer can according to claim 1, wherein,
the Fe-Ni diffusion layer has a thickness of 0.01 [ mu ] m or more and less than 0.5 [ mu ] m.
3. A can for a battery can having Fe-Ni diffusion layers on the surface layers of the inner and outer surfaces of a steel plate in the shape of the can for a battery can,
further having a Ni layer on the Fe-Ni diffusion layer on the outer surface side of the steel sheet,
a part of the Fe-Ni diffusion layer on the outer surface side of the steel sheet was an adhesion amount in terms of Ni conversion of 200mg/m per each surface of the steel sheet 2 ～500mg/m 2 Is provided with a Fe-Ni diffusion layer A,
the Ni ratio at the outermost surface of the Fe-Ni diffusion layer A is 1.0% or more and less than 20.0%,
the Ni ratio is a ratio of the Ni amount at the outermost surface of the Fe-Ni diffusion layer with respect to a total amount of Fe amount and Ni amount in atomic%.
4. The battery can according to claim 3, wherein,
the Fe-Ni diffusion layer A has a thickness of 0.01 μm or more and less than 0.5 μm.
5. The battery can according to claim 3 or 4, wherein,
the thickness of the Ni layer is 1 μm or more.
6. A battery comprising the can of any one of claims 3 to 5, an electrolyte disposed in the can, an electrode, and a separator.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-125251 | 2016-06-24 | ||
| JP2016125251 | 2016-06-24 | ||
| PCT/JP2017/021760 WO2017221763A1 (en) | 2016-06-24 | 2017-06-13 | Steel sheet for battery outer cylindrical canister, battery outer cylindrical canister, and battery |
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| Publication Number | Publication Date |
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| CN109072449A CN109072449A (en) | 2018-12-21 |
| CN109072449B true CN109072449B (en) | 2023-07-14 |
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| CN201780027816.5A Active CN109072449B (en) | 2016-06-24 | 2017-06-13 | Steel plate for outer can of battery, outer can of battery and battery |
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| Country | Link |
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| JP (1) | JP6260752B1 (en) |
| CN (1) | CN109072449B (en) |
| TW (1) | TWI650892B (en) |
| WO (1) | WO2017221763A1 (en) |
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| KR102339193B1 (en) * | 2017-07-28 | 2021-12-13 | 제이에프이 스틸 가부시키가이샤 | Steel plate for battery cans, cans and batteries |
| US11946121B2 (en) | 2017-07-28 | 2024-04-02 | Jfe Steel Corporation | Steel sheet for battery outer tube cans, battery outer tube can and battery |
| EP3808878A4 (en) * | 2018-08-29 | 2021-08-25 | JFE Steel Corporation | Steel sheet for cans, and method for producing same |
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| JP2002212778A (en) * | 2001-01-19 | 2002-07-31 | Nippon Steel Corp | Ni PLATED STEEL SHEET FOR POSITIVE ELECTRODE CAN OF ALKALI MANGANESE BATTERY HAVING EXCELLENT BATTERY CHARACTERISTIC, AND PRODUCTION METHOD THEREFOR |
| CN101501884A (en) * | 2006-08-09 | 2009-08-05 | 松下电器产业株式会社 | Battery can and battery using the same |
| JP2009263727A (en) * | 2008-04-25 | 2009-11-12 | Nippon Steel Corp | Ni-PLATED STEEL SHEET FOR CONTAINER, CONTAINER MANUFACTURED FROM THE SAME AND MANUFACTURING METHOD THEREFOR |
| CN102763237A (en) * | 2010-01-08 | 2012-10-31 | 东洋钢钣株式会社 | Ni-plated steel sheet with excellent pressability for battery can |
| CN105164321A (en) * | 2013-04-30 | 2015-12-16 | 新日铁住金株式会社 | Ni-plated steel sheet, and method for producing Ni-plated steel sheet |
| CN105283584A (en) * | 2013-05-21 | 2016-01-27 | 新日铁住金株式会社 | Steel sheet for container, and method for producing steel sheet for container |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6168826B2 (en) * | 2013-04-12 | 2017-07-26 | 東洋鋼鈑株式会社 | Steel with Mn layer |
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2017
- 2017-06-13 WO PCT/JP2017/021760 patent/WO2017221763A1/en active Application Filing
- 2017-06-13 JP JP2017544977A patent/JP6260752B1/en active Active
- 2017-06-13 CN CN201780027816.5A patent/CN109072449B/en active Active
- 2017-06-21 TW TW106120781A patent/TWI650892B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002212778A (en) * | 2001-01-19 | 2002-07-31 | Nippon Steel Corp | Ni PLATED STEEL SHEET FOR POSITIVE ELECTRODE CAN OF ALKALI MANGANESE BATTERY HAVING EXCELLENT BATTERY CHARACTERISTIC, AND PRODUCTION METHOD THEREFOR |
| CN101501884A (en) * | 2006-08-09 | 2009-08-05 | 松下电器产业株式会社 | Battery can and battery using the same |
| JP2009263727A (en) * | 2008-04-25 | 2009-11-12 | Nippon Steel Corp | Ni-PLATED STEEL SHEET FOR CONTAINER, CONTAINER MANUFACTURED FROM THE SAME AND MANUFACTURING METHOD THEREFOR |
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| CN105164321A (en) * | 2013-04-30 | 2015-12-16 | 新日铁住金株式会社 | Ni-plated steel sheet, and method for producing Ni-plated steel sheet |
| CN105283584A (en) * | 2013-05-21 | 2016-01-27 | 新日铁住金株式会社 | Steel sheet for container, and method for producing steel sheet for container |
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| Publication number | Publication date |
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| JP6260752B1 (en) | 2018-01-17 |
| WO2017221763A1 (en) | 2017-12-28 |
| TWI650892B (en) | 2019-02-11 |
| JPWO2017221763A1 (en) | 2018-06-28 |
| TW201813158A (en) | 2018-04-01 |
| CN109072449A (en) | 2018-12-21 |
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