CN114540604B - Nickel-plated steel strip for battery container and preparation method thereof - Google Patents
Nickel-plated steel strip for battery container and preparation method thereof Download PDFInfo
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- CN114540604B CN114540604B CN202210167515.5A CN202210167515A CN114540604B CN 114540604 B CN114540604 B CN 114540604B CN 202210167515 A CN202210167515 A CN 202210167515A CN 114540604 B CN114540604 B CN 114540604B
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
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- C21D1/26—Methods of annealing
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- C—CHEMISTRY; METALLURGY
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0273—Final recrystallisation annealing
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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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
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
- H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
- H01M50/222—Inorganic material
- H01M50/224—Metals
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- 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
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- 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
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Abstract
The invention discloses a preparation method of a nickel-plated steel strip for a battery container, and relates to the technical field of steel strip processing. According to the invention, the low-carbon alloy steel strip is pretreated and then is subjected to cold rolling treatment, the cold-rolled steel strip is plated with nickel, finally, the cold-rolled steel strip is subjected to continuous annealing treatment and heat treatment in sequence, and then the cover annealing treatment is adopted for overaging treatment, so that the treated nickel-plated steel strip does not need to be subjected to high-pressure flattening treatment, and the nickel-plated steel strip with more excellent comprehensive mechanical properties is obtained.
Description
Technical Field
The invention belongs to the technical field of steel strip processing, and particularly relates to a nickel-plated steel strip for a battery container and a preparation method thereof.
Background
The nickel pre-plated steel strip for the battery container is a battery steel strip which is subjected to heat treatment after continuous nickel plating on the surface of the steel strip to generate a nickel-iron alloy layer. In the process of preparing the battery, the nickel pre-plated steel strip can be directly punched into a shell and further processed into the battery. Compared with the prior art that the barrel plating is carried out after the steel strip of the common battery is punched into the shell. The nickel pre-plated steel strip has better nickel layer adhesion, excellent nickel layer uniformity and good tensile and pressure-bearing capacity, and a traditional rear nickel-plated steel shell cannot be effectively plated on the inner wall of the steel shell in the barrel plating process, while the inner wall of the nickel pre-plated steel shell has a stable and effective nickel layer, so that the steel shell has longer service life and stability after being prepared into the steel shell. Therefore, the preparation of lithium batteries by nickel pre-plated steel strips has become the current mainstream.
The prior preparation process of the nickel-plated steel strip needs annealing and overaging treatment. The main purpose of the overaging treatment is to precipitate supersaturated solid-dissolved carbon atoms in the recrystallization annealing process after rapid cooling in the form of carbides or the like in a natural way or an artificial heating way. The overaging treatment is insufficient, and solid-solution carbon atoms and dislocations are easy to form Coriolis air masses, so that the obvious yield phenomenon of the material is caused, and the material can be represented as an obvious yield platform on a tensile curve.
The continuous annealing equipment enables the time for overaging treatment by adopting the continuous annealing equipment to be shorter based on factors such as site, equipment manufacturing cost and the like, so that the treated nickel pre-plated steel strip still contains partial solid solution carbon atoms, and the solid solution carbon atoms are easy to form Coriolis gas clusters with dislocations to cause the yield phenomenon of metals. Therefore, the pre-nickel-plated steel strip after the overaging treatment needs to be subjected to a large pressure leveling treatment to eliminate the influence of the Coriolis gas cluster, the large pressure leveling treatment not only can cause the yield strength of the material to be too high and reduce the anisotropy of the material, but also can generate a certain internal stress on a nickel layer, and the prepared nickel-plated steel strip cracks or the nickel layer falls off in the using process.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides the preparation method of the nickel-plated steel strip for the battery container, the nickel-plated steel strip can be subjected to full overaging treatment without being subjected to high-pressure leveling treatment, solid-solution carbon atoms in the nickel-plated steel strip are fully precipitated, and the stability of the nickel-plated steel strip is improved.
A preparation method of a nickel-plated steel strip for a battery container comprises the following specific steps:
(1) Carrying out oil removal and acid washing pretreatment on the low-carbon alloy steel strip;
(2) Carrying out cold rolling treatment on the pretreated low-carbon alloy steel strip, wherein the cold rolling reduction rate is controlled to be 80-90%;
(3) Carrying out nickel plating treatment on the cold-rolled low-carbon alloy steel strip, and controlling the thickness of a nickel layer on one side of the steel strip to be 2.5-3.5 mu m and the thickness of the nickel layer on the other side of the steel strip to be 0.8-1.5 mu m;
(4) Continuously annealing the nickel-plated low-carbon alloy steel strip at 700-780 ℃ for 60-90 s;
(5) Performing overaging treatment on the steel strip treated in the step (4) by using a hood-type annealing furnace, wherein the overaging temperature is 300-380 ℃, and the overaging time is 5-8 h;
(6) Flattening the nickel-plated steel strip after the overaging treatment, wherein the flattening pressure is 6-8 Mpa;
(7) And shearing, packaging and warehousing the flattened nickel-plated steel strip.
Preferably, the low-carbon alloy steel strip in the step (1) of the invention is low-carbon aluminum killed steel with the carbon content of 0.012-0.08% or interstitial free steel (IF steel) with the ultralow carbon content and doped with elements such as Ti, nb and the like. The low-carbon aluminum killed steel is preferably selected, wherein the low-carbon alloy steel strip adopted by the invention comprises the following main elements in percentage by mass:
c:0.05%, si:0.014%, mn:0.25%, P:0.007%, S:0.008%, solAl:0.05%, cr:0.065%, and the balance of iron and inevitable impurities.
Preferably, the nickel solution used in the nickel plating in the step (2) contains 200-500g/L of nickel sulfate, 30-60g/L of nickel chloride and 30-60g/L of boric acid.
More preferably, the pH of the nickel liquid is 3 to 5, and preferably 4.
Preferably, the nickel plating temperature is 50-60 ℃, and the current density is 5-20A/dm 2 。
Another object of the present invention is to provide a nickel-plated steel strip for battery containers, which has a structure as shown in fig. 2, and the nickel-plated steel strip of the present invention includes a steel strip body 11, and a nickel layer 14 and a nickel layer 15 located on both sides of the steel strip body 11, wherein a nickel-iron alloy layer 12 is formed between the steel strip body 11 and the nickel layer 14, and a nickel-iron alloy layer 13 is formed between the steel strip body 11 and the nickel layer 15.
Preferably, the method utilizes an edxrfspecrometer to measure the thickness of the nickel layer, one point is taken at intervals of 1cm in the transverse direction of the steel strip to detect the thickness, and finally the average value is taken as the thickness of the nickel layer. The thickness of the nickel layer 14 is 2.5-3.5 μm, and the thickness of the nickel layer 15 is 0.8-1.5 μm. Wherein, the direction of the nickel layer 14 is used as the outer wall of the steel shell in the process of punching the battery shell and is also called as the A surface of the nickel preplated steel strip, and the direction of the nickel layer 15 is used as the inner wall of the steel shell and is also called as the B surface of the nickel preplated steel strip.
Preferably, the thickness of the nickel-iron alloy layer is detected to find that the thickness of the too thin nickel-iron alloy layer is too thin, the surface still has more pure nickel layers, the hardness of the nickel-iron alloy layer is larger than that of a steel base belt, the nickel-iron alloy layer is easy to crack after the working procedures of stretching, rolling groove and the like, the steel base belt is easy to directly contact with electrolyte in a battery, and the corrosion resistance of the steel shell after the steel shell is assembled into the battery is poor. And the too thick ferronickel alloy layer can cause iron element to diffuse to the surface, and the iron leakage rate is higher. After the battery is assembled, iron easily permeates into electrolyte to generate a pitting phenomenon, and more gases are generated seriously to influence the service life of the battery. Preferably, the thickness of the ferronickel alloy layer 12 is 0.8 to 1.2 μm, and the thickness of the ferronickel alloy layer 13 is 0.6 to 0.9 μm.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a nickel-plated steel strip for a battery container and a preparation method thereof. Wherein the purpose of the continuous annealing is to achieve a recrystallization process of the steel base strip and a diffusion process between the nickel plating and the steel base strip. The rapid temperature rise and temperature reduction of the continuous annealing can obtain finer structure grains, so that the comprehensive mechanical property of the steel base band is more excellent. The continuous annealing can also avoid mutual adhesion between steel belts in the cover type annealing process, and improve the surface quality of the steel belts. The bell-type annealing can ensure that the steel strip has sufficient overaging, a large-pressure flattening process can be omitted in the follow-up process, the steel strip has no yield phenomenon, and the steel strip has good anisotropy and good deep drawing performance.
Drawings
FIG. 1 is a steel strip structure after nickel plating according to the present invention;
description of the sequence numbers: 11 is a steel strip body, and 14 is a nickel layer on one side of the steel strip; 15 is a nickel layer on the other side of the steel strip;
FIG. 2 is a steel strip structure after annealing according to the invention;
description of the sequence numbers: 12 and 13 are both nickel-iron alloy layers.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A preparation method of a nickel-plated steel strip for a battery container comprises the following specific steps:
(1) Carrying out oil removal and acid washing treatment on the low-carbon alloy steel strip; the low-carbon alloy steel strip comprises the following main elements in percentage by mass:
c:0.05%, si:0.014%, mn:0.25%, P:0.007%, S:0.008%, solAl:0.05%, cr:0.065%, and the balance of iron and inevitable impurities.
(2) Carrying out cold rolling treatment on the pretreated low-carbon alloy steel strip, wherein the cold rolling reduction rate is controlled to be 80%;
(3) Carrying out nickel plating treatment on the cold-rolled low-carbon alloy steel strip, wherein the nickel solution contains 350g/L nickel sulfate, 45g/L nickel chloride and 40g/L boric acid, the pH value of the nickel solution is 4, the temperature is 55 ℃, and the current density is 10A/dm 2 Then nickel plating is carried out; obtaining a nickel pre-plated steel strip, as shown in fig. 1, in which the nickel layer 14 has an average thickness of 3.25 μm and the nickel layer 15 has an average thickness of 1.19 μm;
(4) Continuously annealing the nickel preplating steel strip at the annealing temperature of 750 ℃ for 70s;
(5) Performing overaging treatment by adopting cover annealing, wherein the overaging temperature is 330 ℃, and the overaging time is 8h;
(6) And (5) flattening the steel strip with the flattening pressure of 6MPa.
(7) And (4) cutting, packaging and warehousing the nickel-plated steel strip after the leveling treatment.
Example 2
A preparation method of a nickel-plated steel strip for a battery container comprises the following steps:
(1) Carrying out oil removal and acid washing treatment on the low-carbon alloy steel strip; the low-carbon alloy steel strip comprises the following main elements in percentage by mass:
c:0.05%, si:0.014%, mn:0.25%, P:0.007%, S:0.008%, solAl:0.05%, cr:0.065%, and the balance of iron and inevitable impurities.
(2) Carrying out cold rolling treatment on the pretreated low-carbon alloy steel strip, wherein the cold rolling reduction rate is controlled to be 85%;
(3) Carrying out nickel plating treatment on the cold-rolled low-carbon alloy steel strip, wherein the nickel solution contains 350g/L of nickel sulfate, 45g/L of nickel chloride and 40g/L of boric acid, the pH value of the nickel solution is 4, the temperature is 55 ℃, and the current density is 10A/dm 2 Then nickel plating is carried out; obtaining a nickel preplated steel strip, as shown in FIG. 1, wherein the average thickness of the nickel layer 14 is finally 3.3 μm, and the average thickness of the nickel layer 15 is finally 1.22 μm;
(4) Continuously annealing the nickel pre-plated steel strip, wherein the annealing temperature is 730 ℃, and the annealing time is 90s;
(5) And performing overaging treatment by adopting cover annealing, wherein the overaging temperature is 350 ℃, and the overaging time is 6h.
(6) And (5) flattening the steel strip with the flattening pressure of 6MPa.
(7) And (4) shearing, packaging and warehousing the nickel-plated steel strip after the leveling treatment.
Example 3
A preparation method of a nickel-plated steel strip for a battery container comprises the following specific steps:
(1) Carrying out oil removal and acid washing treatment on the low-carbon alloy steel strip; the low-carbon alloy steel strip comprises the following main elements in percentage by mass:
c:0.05%, si:0.014%, mn:0.25%, P:0.007%, S:0.008%, solAl:0.05%, cr:0.065%, and the balance of iron and inevitable impurities.
(2) Carrying out cold rolling treatment on the pretreated low-carbon alloy steel strip, wherein the cold rolling reduction rate is controlled at 90%;
(3) Carrying out nickel plating treatment on the cold-rolled low-carbon alloy steel strip, wherein the nickel solution contains 350g/L of nickel sulfate, 45g/L of nickel chloride and 40g/L of boric acid, the pH value of the nickel solution is 4, the temperature is 55 ℃, and the current density is 10A/dm 2 Then nickel plating is carried out; obtaining a nickel preplated steel strip, as shown in FIG. 1, in which the nickel layer 14 has an average thickness of 3.28 μm and the nickel layer 15 has an average thickness of 1.18 μm;
(4) Continuously annealing the nickel preplating steel strip at 780 ℃ for 50s;
(5) And performing failure treatment by adopting cover annealing, wherein the aging temperature is 380 ℃, and the aging time is 5h.
(6) And flattening the steel strip with the flattening pressure of 6MPa.
(7) And (4) shearing, packaging and warehousing the nickel-plated steel strip after the leveling treatment.
Comparative example 1
A preparation method of a nickel-plated steel strip for a battery container comprises the following specific steps:
(1) Carrying out oil removal and acid washing treatment on the low-carbon alloy steel strip; the low-carbon alloy steel strip comprises the following main elements in percentage by mass:
c:0.05%, si:0.014%, mn:0.25%, P:0.007%, S:0.008%, solAl:0.05%, cr:0.065%, and the balance of iron and inevitable impurities.
(2) Carrying out cold rolling treatment on the pretreated low-carbon alloy steel strip, wherein the cold rolling reduction rate is controlled to be 60%;
(3) Carrying out nickel plating treatment on the cold-rolled low-carbon alloy steel strip, wherein the nickel solution contains 350g/L of nickel sulfate, 45g/L of nickel chloride and 40g/L of boric acid, the pH value of the nickel solution is 4, the temperature is 55 ℃, and the current density is 10A/dm 2 Then nickel plating is carried out; obtaining the nickel preplating steel strip, wherein the average thickness of the nickel layer 14 is finally 3.31 mu m, and the average thickness of the nickel layer 15 is finally 1.19 mu m;
(4) Continuously annealing the nickel preplating steel strip at the annealing temperature of 750 ℃ for 70s;
(5) Performing overaging treatment by adopting cover annealing, wherein the overaging temperature is 330 ℃, and the overaging time is 8h;
(6) And (5) flattening the steel strip with the flattening pressure of 6MPa.
(7) And (4) cutting, packaging and warehousing the nickel-plated steel strip after the leveling treatment.
Comparative example 2
A preparation method of a nickel-plated steel strip for a battery container comprises the following specific steps:
(1) Carrying out oil removal and acid washing treatment on the low-carbon alloy steel strip; the low-carbon alloy steel strip comprises the following main elements in percentage by mass:
c:0.05%, si:0.014%, mn:0.25%, P:0.007%, S:0.008%, solAl:0.05%, cr:0.065%, and the balance of iron and inevitable impurities.
(2) Carrying out cold rolling treatment on the pretreated low-carbon alloy steel strip, wherein the cold rolling reduction rate is controlled to be 90%;
(3) Carrying out nickel plating treatment on the cold-rolled low-carbon alloy steel strip, wherein the nickel solution contains 350g/L of nickel sulfate, 45g/L of nickel chloride and 40g/L of boric acid, the pH value of the nickel solution is 4, the temperature is 55 ℃, and the current density is 10A/dm 2 Then nickel plating is carried out; obtaining the nickel preplating steel strip, wherein the average thickness of the nickel layer 14 is finally 3.31 mu m, and the average thickness of the nickel layer 15 is finally 1.19 mu m;
(4) Continuously annealing the nickel preplating steel strip at the annealing temperature of 750 ℃ for 70s;
(5) Performing overaging treatment by adopting cover annealing, wherein the overaging temperature is 330 ℃, and the overaging time is 8h;
(6) And flattening the steel strip with the flattening pressure of 6MPa.
(7) And (4) cutting, packaging and warehousing the nickel-plated steel strip after the leveling treatment.
Comparative example 3
A preparation method of a nickel-plated steel strip for a battery container comprises the following steps:
(1) Carrying out oil removal and acid washing treatment on the low-carbon alloy steel strip; the low-carbon alloy steel strip comprises the following main elements in percentage by mass:
c:0.05%, si:0.014%, mn:0.25%, P:0.007%, S:0.008%, solAl:0.05%, cr:0.065%, and the balance of iron and inevitable impurities.
(2) Carrying out cold rolling treatment on the pretreated low-carbon alloy steel strip, wherein the cold rolling reduction rate is controlled at 80%;
(3) Carrying out nickel plating treatment on the cold-rolled low-carbon alloy steel strip, wherein the nickel solution contains 350g/L of nickel sulfate, 45g/L of nickel chloride and 40g/L of boric acid, the pH value of the nickel solution is 4, the temperature is 55 ℃, and the current density is 10A/dm 2 Then nickel plating is carried out; obtaining a nickel preplated steel strip, as shown in FIG. 1Shown therein, wherein the average thickness of nickel layer 14 was finally 3.25 μm and the average thickness of nickel layer 15 was finally 1.19 μm;
(5) Carrying out overaging treatment by adopting continuous annealing, wherein the overaging temperature is 330 ℃, and the overaging time is 120s;
(6) And flattening the steel strip with the flattening pressure of 20MPa.
(7) And (4) flattening, shearing, packaging and warehousing the nickel-plated steel strip after the flattening treatment.
The steel strip products prepared in the examples 1 to 3 and the comparative examples 1 to 3 are subjected to alloy layer thickness detection, XRD detection and punching to form 18650 battery steel shells, and then are subjected to rolling groove according to requirements. The nickel layer was tested for pressure resistance and corrosion resistance and the results are summarized in table 1.
TABLE 1
According to the standard GB/T5027-2016, the nickel pre-plated steel strip is subjected to plastic strain ratio (r) and anisotropy value (delta r) detection in a tensile testing machine;
the reject ratio: the steel strip is punched into 18650 steel casings and channelled as required by the cell. Observing the state of the nickel layer at the rolling groove under a 200-time microscope, and counting the defect rate.
Rolling groove defect rate = number of nickel layer cracks at rolling groove/total count
And (3) corrosion resistance test: neutral salt spray test, in a specific test box (electroplating equipment), spraying saline water containing (5 Shi 0.5)% of sodium chloride and having a pH value of 6.5-7.2 by a spraying device, so that the salt spray is settled on a test piece to be tested, and observing the surface corrosion state of the test piece after a certain period of time. The temperature of the test chamber is required to be (35 +/-2) DEG C, the humidity is more than 95 percent, and the fog reduction amount is 1-2 mL/(h cm) 2 ) The nozzle pressure is 78.5 to 137.3kPa (0.8 to 1.4 kgf/cm) 2 ). Spraying for 8 hr, and soaking for 16 hrWhen the user wants to use the device. The rating is carried out according to GB/T6461-2002.
The thickness of the nickel-iron alloy layer was measured by means of a Horiba high-frequency glow discharge spectrometer by continuously measuring the Fe intensity and the Ni intensity in the depth direction from the surface of the nickel-preplated steel strip after heat treatment, the depth at which the Fe intensity showed 20% of its saturation value was D1, and the depth at which the Ni intensity showed 20% of its saturation value was D2. And (D2-D1) is the thickness of the nickel-iron alloy layer.
As can be seen from Table 1, the nickel-plated steel strip obtained by the comparative example 1, which is treated with a low cold rolling reduction, has a low r value, a low alloy layer thickness and poor corrosion resistance, and thus has a high punching defect rate. In comparative example 2, the higher cold rolling reduction ratio was used, so that the r value of the nickel-plated steel strip was higher, but the anisotropy was poor, and the punching defect rate of the nickel-plated steel strip was also increased.
Comparative example 3 the nickel-plated steel strip is prepared by adopting the traditional continuous annealing and pressure-increasing flattening process, the r value of the steel strip is greatly different from that of the steel strip in example 1, and the performance of the nickel-plated steel strip prepared in comparative example 3 is far lower than that of the nickel-plated steel strip prepared in example 1 of the invention.
It should be noted that the above-mentioned embodiments are merely examples of the present invention, and it is obvious that the present invention is not limited to the above-mentioned embodiments, and other modifications are possible. All modifications directly or indirectly derivable by a person skilled in the art from the present disclosure are to be considered within the scope of the present invention.
Claims (6)
1. A preparation method of a nickel-plated steel strip for a battery container is characterized by comprising the following specific steps:
(1) Carrying out oil removal and acid washing pretreatment on the low-carbon alloy steel strip;
(2) Carrying out cold rolling treatment on the pretreated low-carbon alloy steel strip, wherein the cold rolling reduction rate is controlled to be 80-90%;
(3) Carrying out nickel plating treatment on the cold-rolled low-carbon alloy steel strip, and controlling the thickness of a nickel layer on one side of the steel strip to be 2.5-3.5 mu m and the thickness of a nickel layer on the other side of the steel strip to be 0.8-1.5 mu m;
(4) Continuously annealing the nickel-plated low-carbon alloy steel strip at the annealing temperature of 700-780 ℃ for 60-90s;
(5) Carrying out overaging treatment on the steel strip treated in the step (4) by using a hood-type annealing furnace, wherein the overaging temperature is 300-380 ℃, and the overaging time is 5-8h;
(6) Flattening the nickel-plated steel strip after overaging treatment, wherein the flattening pressure is 6-8 MPa;
(7) Shearing, packaging and warehousing the flattened nickel-plated steel strip;
the low-carbon alloy steel strip in the step (1) comprises the following main elements in percentage by mass:
c:0.05%, si:0.014%, mn:0.25%, P:0.007%, S:0.008%, solAl:0.05%, cr:0.065%, and the balance of iron and inevitable impurities;
the nickel solution adopted by the nickel plating in the step (2) contains 200-500g/L of nickel sulfate, 30-60g/L of nickel chloride and 30-60g/L of boric acid.
2. The method for producing a nickel-plated steel strip for battery containers as claimed in claim 1, wherein the plating solution has a pH of 3 to 5.
3. The method for producing a nickel-plated steel strip for battery containers as claimed in claim 2, wherein the nickel plating temperature is 50 to 60 ℃ and the current density is 5 to 20A/dm 2 。
4. A nickel-plated steel strip for battery containers, which is prepared by the method of claims 1 to 3, and comprises a steel strip body (11), and a nickel layer (14) and a nickel layer (15) which are arranged on two sides of the steel strip body (11), wherein a nickel-iron alloy layer (12) is formed between the steel strip body (11) and the nickel layer (14), and a nickel-iron alloy layer (13) is formed between the steel strip body (11) and the nickel layer (15).
5. The nickel-plated steel strip for battery containers according to claim 4, wherein the thickness of the nickel layer (14) is 2.5 to 3.5 μm, and the thickness of the nickel layer (15) is 0.8 to 1.5 μm.
6. The nickel-plated steel strip for battery containers according to claim 5, wherein the thickness of the nickel-iron alloy layer (12) is 0.8 to 1.2 μm, and the thickness of the nickel-iron alloy layer (13) is 0.6 to 0.9 μm.
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