CN115786913A - Battery steel shell with metal layer plated on surface and processing technology thereof - Google Patents
Battery steel shell with metal layer plated on surface and processing technology thereof Download PDFInfo
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Abstract
The invention relates to the technical field of battery steel shells, in particular to a battery steel shell with a metal layer plated on the surface and a processing technology thereof. The method comprises the following steps: step 1: polishing the surface of the low-carbon steel strip, performing alkali washing, acid washing and water washing, placing the low-carbon steel strip in a Ni-Fe plating solution, and electroplating to obtain a Ni-Fe metal layer which is a steel strip A; and 2, step: performing magnetron sputtering on the surface of the steel strip A to obtain Ni-Fe-Co, wherein the alloy target is Ni-Fe10at% -Co10at%, and the technological parameters are as follows: 2 to 5T of external magnetic field, 30 to 50W of sputtering power and 0.03 to 0.05nm/s of deposition rate; obtaining a Ni-Fe-Co metal layer which is a steel strip B; and 3, step 3: placing the steel strip B in a Ni-Fe-Co-P plating solution, and electroplating to obtain a Ni-Fe-Co-P metal layer and obtain a steel strip C; and 4, step 4: and annealing, aging and flattening the steel strip C to obtain a battery steel strip, and punching to obtain a battery steel shell. In the technical scheme, the proportion of metal in each layer is set in a gradient manner by optimizing the plated metal layer, so that the thickness is reduced, and the stamping performance is improved, thereby improving the physical stability, the pressure resistance and the corrosion resistance of the battery steel shell.
Description
Technical Field
The invention relates to the technical field of battery steel shells, in particular to a battery steel shell with a metal layer plated on the surface and a processing technology thereof.
Background
In recent years, the adjustment of energy structures makes the technical development and application of new energy vehicles more and more emphasized, which also makes the power battery composition as the core of new energy vehicles a focus of research objects. Among them, the battery case is a main medium for protecting the internal materials of the battery from damage and securing the usability and safety of the battery, and thus is required to have high physical stability and punching properties.
At present, battery shells are generally divided into aluminum shells and steel shells, although the aluminum shells have good corrosion resistance, plasticity and processing formability; however, compared with a steel shell, the physical stability and the pressure resistance of the lithium ion battery are far lower than those of the steel shell, so that the steel shell is mainly used in a common column type lithium battery, and the safety is higher. The steel shell is usually mainly made of stainless steel and low-carbon steel; since stainless steel is not suitable for a stamping process, most studies have been made on low carbon steel, and generally, in order to enhance corrosion resistance, the nickel plating layer is used to improve corrosion resistance and stamping resistance. In the prior art, the battery shell is not high in overall hardness, and is mostly obtained by a stamping process, so that cracks or plating layers fall off in the stamping process, and the pressure resistance and the corrosion resistance are reduced. On the other hand, a thick metal layer is generally plated to enhance corrosion resistance, but the thick metal layer has disadvantages such as an increase in raw material cost and a decrease in punching property.
In conclusion, the preparation of a steel battery shell with a metal layer plated on the surface is of great value in solving the problems.
Disclosure of Invention
The invention aims to provide a steel battery shell with a metal layer plated on the surface and a processing technology thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a processing technology of a battery steel shell with a metal layer plated on the surface comprises the following steps:
step 1: polishing, alkali washing, acid washing and water washing the surface of the low-carbon steel strip, placing the low-carbon steel strip in Ni-Fe plating solution, and electroplating to obtain a Ni-Fe metal layer which is a steel strip A;
and 2, step: carrying out magnetron sputtering on the surface of the steel strip A to obtain a Ni-Fe-Co metal layer, namely a steel strip B;
and step 3: placing the steel strip B in a Ni-Fe-Co-P plating solution, and electroplating to obtain a Ni-Fe-Co-P metal layer to obtain a steel strip C;
and 4, step 4: and annealing, aging and flattening the steel strip C to obtain a battery steel strip, and punching to obtain a battery steel shell.
Optimally, the thickness of the Ni-Fe metal layer is 0.6 to 1 mu m; the thickness of the Ni-Fe-Co metal layer is 0.12 to 0.17 mu m; the thickness of the Ni-Fe-Co-P metal layer is 2.5 to 3.5 mu m.
Preferably, in the step 2, in the technological process of magnetron sputtering Ni-Fe-Co, the alloy target material is Ni-Fe10at% -Co10at%; the technological parameters are as follows: an external magnetic field is 2 to 5T, the sputtering power is 30 to 50W, and the deposition rate is 0.03 to 0.05nm/s.
Preferably, in step 1, the Ni-Fe plating solution comprises the following components: 100-120g/L of nickel sulfate, 30-40g/L of boric acid, 20-30g/L of ferric sulfate, 10-20g/L of lactic acid, 10-20g/L of sodium lactate, 0.1-0.2g/L of sodium dodecyl sulfate and 0.8-0.9g/L of saccharin;
the electroplating process parameters of the Ni-Fe metal layer are as follows: the temperature is 40 to 50 ℃, and the current density is 3 to 4A/dm 2 The plating time was 160 to 240 seconds.
Preferably, in step 3, the components of the Ni-Fe-Co-P plating solution include the following: 100-120g/L of nickel sulfate, 30-35g/L of boric acid, 18-20g/L of ferric sulfate, 10-12g/L of cobalt chloride, 20-25g/L of nickel chloride, 20-30g/L of phosphoric acid, 10-20g/L of lactic acid, 0.1-0.2g/L of sodium dodecyl sulfate, 0.01-0.015g/L of thiourea, 1-1.2g of acidic sol and 0.3-0.5g/L of graphene oxide.
Preferably, the acidic sol is a mixed sol of titanium dioxide and cerium dioxide; the method comprises the following specific steps: dispersing ammonium ceric nitrate in an aqueous solution, heating to 90-95 ℃, adding titanium tetrachloride, stirring and aging for 2 hours to obtain an acidic sol; the mass ratio of the ammonium ceric nitrate to the titanium tetrachloride is (1.5-2) 1. The aqueous solution is an aqueous solution containing an organic acid catalyst; organic acid catalysts include, but are not limited to, lactic acid or hydrochloric acid.
Preferably, in step 3, the electroplating process parameters of the Ni-Fe-Co-P metal layer are as follows: the temperature is 45 to 55 ℃, and the current density is increased to 4 to 6A/dm at the speed of 0.5A/min 2 The total plating time is 600 to 840 seconds.
Optimally, in the step 4, the annealing temperature is 700 to 780 ℃ and the time is 60 to 90 seconds; the aging temperature is 300 to 350 ℃, the time is 6 to 10 hours, and the leveling pressure is 6 to 8Mpa.
Preferably, the battery steel shell is prepared by a processing technology of the battery steel shell with the metal layer plated on the surface.
In the technical scheme, the metal layers plated on the surfaces are optimized, the proportion of metal in each layer is set in a gradient manner, the thickness is reduced, and the stamping performance is improved, so that the physical stability, the pressure resistance and the corrosion resistance of the battery steel shell are improved.
In the scheme, the metal layers plated on the surfaces comprise a Ni-Fe metal layer, a Ni-Fe-Co metal layer and a Ni-Fe-Co-P metal layer; the gradient difference of each metal between the three layers is utilized, firstly, the potential difference between the layers can be caused by utilizing the gradient difference, so that the corrosion resistance is inhibited, the thickness of the metal layer is reduced, and the corrosion resistance is ensured; on the other hand, gradient difference is utilized to combine layer by layer, so that the adhesive force between metal layers and between the metal layers and the low-carbon steel is improved, the peeling phenomenon in the stamping process is inhibited, and the crack phenomenon is inhibited through the matching between layers; thereby improving the comprehensive performance of the battery steel shell.
Wherein, the Ni-Fe metal layer is arranged for connecting the Ni-Fe-Co metal layer in a gradient way, the iron content in the layer is about 7wt% (higher), the Ni-Fe metal layer has similarity with the iron in the low-carbon steel, and the interface acting force is strong. On the other hand, the Ni-Fe metal layer has the greatest advantages of excellent ductility and toughness, and can effectively inhibit interface cracks and falling-off phenomena in the stamping process. Is a good material for connecting the metal layer and the low-carbon steel.
On one hand, the iron content in the Ni-Fe-Co metal layer intermediate layer is about 10wt% (the content is lower than that of the Ni-Fe metal layer, and the corrosion resistance is higher than that of the Ni-Fe metal layer), so that the Ni-Fe-Co metal layer intermediate layer has good interface adhesion and can inhibit cracks. Meanwhile, cobalt is introduced into the layer, and the performance of cobalt is similar to that of nickel, so that the cobalt has good toughness; secondly, the introduction of cobalt can improve the corrosion resistance, enhance the corrosion resistance and avoid pitting corrosion.
On the other hand, in the deposition process of the layer, the layer is used as an enhancement layer through effective control of magnetron sputtering, a magnetic field and thickness, so that the hardness and the stamping performance of the battery steel shell are effectively improved, and the safety of the battery is effectively improved. Specifically, the method comprises the following steps: compared with a crystalline plating layer obtained by an electroplating process, the nickel obtained by magnetron sputtering is amorphous, and has better strength, firmness, compactness and uniformity; meanwhile, the arrangement of the external magnetic field promotes the magnetic anisotropy of the deposition layer, improves the mechanical property and effectively improves the stamping property. In addition, the thickness is easier to control by magnetron sputtering, so that the deposition thickness is changed to be thinner as an enhancement layer; and the increase of the thickness of the steel shell can increase the residual stress and reduce the dissimilarity between layers, so that the performance of the steel shell of the battery is reduced.
The Ni-Fe-Co-P metal layer is used as the last metal layer, so that the corrosion resistance is better, and the residual stress of the magnetron sputtering layer can be effectively reduced; meanwhile, the surface hardness is improved, and the scratch resistance of the surface is improved. Phosphorus is further introduced into the layer, further enhancing wear and corrosion resistance. And the increase of the composite sol of titanium dioxide and cerium dioxide and graphene oxide further improves the compactness of the surface layer, inhibits the impurity pores and improves the corrosion resistance. The composite sol enhances the dispersibility of the graphene oxide, plays a role in codeposition and adhesion to the graphene oxide, and can balance relative conductivity, enhance the uniformity of the alloy in the coating and inhibit the appearance of larger or prominent grains due to the introduction of the two. In addition, in the electroplating process, the Ni-Fe-Co-P metal layer presents gradient property by raising current at a constant speed, so that the distribution of interface stress in the loading process is enhanced, the stamping performance is improved, and the delamination or cracking of the interface is effectively inhibited. Meanwhile, the hardness of the surface layer is ensured, and excellent wear resistance and scratch resistance are generated.
Through the arrangement of the three layers, the stamping forming and the corrosion resistance of the battery steel shell after the metal layer is plated are improved in a synergistic manner.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the following examples, the low carbon steel strip was of type Q195; the graphene oxide has a product number of G139803, an oxygen content of 30-40% and a size of 0.5-3 μm, and is provided by Shanghai Aladdin Biotechnology Ltd. The Ni-Fe10at% -Co10at% alloy target is provided by the new promotion material. In the acidic sol, the aqueous solution is an aqueous solution containing an organic acid catalyst, and specifically: 5g of lactic acid was dissolved in 95g of deionized water to obtain an aqueous solution.
Example 1: step 1: the surface of a low-carbon steel strip is polished by 600-mesh sand paper, ultrasonically cleaned by acetone for 20 minutes, washed by deionized water, ultrasonically cleaned by 3wt% of sodium hydroxide for 15 minutes, ultrasonically cleaned by 5wt% of sulfuric acid for 15 minutes, washed by deionized water, and placed in Ni-Fe plating solution at the temperature of 45 ℃ and the current density of 4A/dm 2 Electroplating for 200 seconds to obtain a Ni-Fe metal layer which is a steel strip A;
wherein the Ni-Fe plating solution comprises 120g/L nickel sulfate, 30g/L boric acid, 20g/L ferric sulfate, 15g/L lactic acid, 15g/L sodium lactate, 0.2g/L sodium dodecyl sulfate and 0.8g/L saccharin;
and 2, step: carrying out magnetron sputtering on the surface of the steel strip A by using an external magnetic field of 4T, sputtering power of 50W, deposition rate of 0.04nm/s and Ni-Fe10at% -Co10at% as an alloy target material to obtain a Ni-Fe-Co metal layer with the thickness of 0.15 mu m;
and step 3: placing the steel strip B in Ni-Fe-Co-P plating solutionAt a temperature of 50 ℃, the current density is raised to 5A/dm at a rate of 0.5A/min 2 Electroplating for 720 seconds to obtain a Ni-Fe-Co-P metal layer and obtain a steel strip C;
the Ni-Fe-Co-P plating solution comprises 100g/L of nickel sulfate, 30g/L of boric acid, 18g/L of ferric sulfate, 12g/L of cobalt chloride, 20g/L of nickel chloride, 25g/L of phosphoric acid, 20g/L of lactic acid, 0.1g/L of sodium dodecyl sulfate, 0.012g/L of thiourea, 1.1g/L of acid sol and 0.4g/L of graphene oxide; the preparation of the acidic sol comprises the following steps: dispersing 2g of ammonium ceric nitrate in 30g of aqueous solution, heating to 92 ℃, adding 1g of titanium tetrachloride, stirring and aging for 2 hours to obtain acid sol;
and 4, step 4: and (3) annealing the steel strip C at 750 ℃ for 60 seconds, aging in a bell-type furnace at 320 ℃ for 8 hours, flattening under 8Mpa to obtain the battery steel strip, and punching to obtain the battery steel shell.
Example 2: step 1: the surface of a low-carbon steel strip is polished by 600-mesh sand paper, ultrasonically cleaned by acetone for 20 minutes, rinsed by deionized water, ultrasonically cleaned by 3wt% of sodium hydroxide for 15 minutes, ultrasonically cleaned by 5wt% of sulfuric acid for 15 minutes, rinsed by deionized water, and placed in Ni-Fe plating solution at the temperature of 45 ℃ and the current density of 4A/dm 2 Electroplating for 200 seconds to obtain a Ni-Fe metal layer which is a steel strip A;
wherein the Ni-Fe plating solution comprises 120g/L nickel sulfate, 30g/L boric acid, 20g/L ferric sulfate, 15g/L lactic acid, 15g/L sodium lactate, 0.2g/L sodium dodecyl sulfate and 0.8g/L saccharin;
step 2: carrying out magnetron sputtering on the surface of the steel strip A by using an external magnetic field of 4T, sputtering power of 50W, deposition rate of 0.04nm/s and Ni-Fe10at% -Co10at% as an alloy target material to obtain a Ni-Fe-Co metal layer with the thickness of 0.15 mu m;
and step 3: placing the steel strip B in Ni-Fe-Co-P plating solution, and increasing the current density to 4A/dm at a rate of 0.5A/min at a temperature of 50 deg.C 2 Electroplating for 600 seconds to obtain a Ni-Fe-Co-P metal layer and obtain a steel strip C;
the Ni-Fe-Co-P plating solution comprises 100g/L of nickel sulfate, 30g/L of boric acid, 18g/L of ferric sulfate, 12g/L of cobalt chloride, 20g/L of nickel chloride, 20g/L of phosphoric acid, 10g/L of lactic acid, 0.1g/L of sodium dodecyl sulfate, 0.01g/L of thiourea, 1g of acid sol and 0.5g/L of graphene oxide; the preparation of the acid sol comprises the following steps: dispersing 1.5g of ammonium ceric nitrate in 30g of aqueous solution, heating to 90 ℃, adding 1g of titanium tetrachloride, stirring and aging for 2 hours to obtain acid sol;
and 4, step 4: and (3) annealing the steel strip C at 750 ℃ for 60 seconds, aging in a bell-type furnace at 320 ℃ for 8 hours, flattening under 8Mpa to obtain the battery steel strip, and punching to obtain the battery steel shell.
Example 3: step 1: the surface of a low-carbon steel strip is polished by 600-mesh sand paper, ultrasonically cleaned by acetone for 20 minutes, rinsed by deionized water, ultrasonically cleaned by 3wt% of sodium hydroxide for 15 minutes, ultrasonically cleaned by 5wt% of sulfuric acid for 15 minutes, rinsed by deionized water, and placed in Ni-Fe plating solution at the temperature of 45 ℃ and the current density of 4A/dm 2 Electroplating for 200 seconds to obtain a Ni-Fe metal layer which is a steel strip A;
wherein the Ni-Fe plating solution comprises 120g/L nickel sulfate, 30g/L boric acid, 20g/L ferric sulfate, 15g/L lactic acid, 15g/L sodium lactate, 0.2g/L sodium dodecyl sulfate and 0.8g/L saccharin;
step 2: performing magnetron sputtering on the surface of the steel strip A by taking Ni-Fe10at% -Co10at% as an alloy target material under the condition of an external magnetic field of 4T and sputtering power of 50W, wherein the deposition rate is 0.04nm/s, so as to obtain a Ni-Fe-Co metal layer with the thickness of 0.15 mu m;
and step 3: the steel strip B is placed in a Ni-Fe-Co-P bath at a temperature of 50 ℃ and a current density is raised to 6A/dm at a rate of 0.5A/min 2 Electroplating for 840 seconds to obtain a Ni-Fe-Co-P metal layer and obtain a steel strip C;
the Ni-Fe-Co-P plating solution comprises 120g/L nickel sulfate, 35g/L boric acid, 20g/L ferric sulfate, 10g/L cobalt chloride, 25g/L nickel chloride, 30g/L phosphoric acid, 20g/L lactic acid, 0.2g/L sodium dodecyl sulfate, 0.015g/L thiourea, 1.2g acid sol and 0.3g/L graphene oxide; the preparation of the acidic sol comprises the following steps: dispersing 2g of ammonium ceric nitrate in 30g of aqueous solution, heating to 95 ℃, adding 1g of titanium tetrachloride, stirring and aging for 2 hours to obtain acid sol;
and 4, step 4: and annealing the steel strip C at 750 ℃ for 60 seconds, aging in a bell-type furnace at 320 ℃ for 8 hours, flattening under 8Mpa to obtain a battery steel strip, and punching to obtain a battery steel shell.
Comparative example 1: the Ni-Fe-Co metal layer was not provided, and the rest was the same as in example 1;
step 1: the surface of a low-carbon steel strip is polished by 600-mesh sand paper, ultrasonically cleaned by acetone for 20 minutes, rinsed by deionized water, ultrasonically cleaned by 3wt% of sodium hydroxide for 15 minutes, ultrasonically cleaned by 5wt% of sulfuric acid for 15 minutes, rinsed by deionized water, and placed in Ni-Fe plating solution at the temperature of 45 ℃ and the current density of 4A/dm 2 Electroplating for 200 seconds to obtain a Ni-Fe metal layer which is a steel strip A;
wherein the Ni-Fe plating solution comprises 120g/L nickel sulfate, 30g/L boric acid, 20g/L ferric sulfate, 15g/L lactic acid, 15g/L sodium lactate, 0.2g/L sodium dodecyl sulfate and 0.8g/L saccharin;
and 2, step: placing the steel strip A in Ni-Fe-Co-P plating solution, and increasing the current density to 5A/dm at a rate of 0.5A/min at a temperature of 50 deg.C 2 Electroplating for 720 seconds to obtain a Ni-Fe-Co-P metal layer and obtain a steel strip B;
the Ni-Fe-Co-P plating solution comprises 100g/L of nickel sulfate, 30g/L of boric acid, 18g/L of ferric sulfate, 12g/L of cobalt chloride, 20g/L of nickel chloride, 25g/L of phosphoric acid, 20g/L of lactic acid, 0.1g/L of sodium dodecyl sulfate, 0.012g/L of thiourea, 1.1g/L of acid sol and 0.4g/L of graphene oxide; the preparation of the acidic sol comprises the following steps: dispersing 2g of ammonium ceric nitrate in 30g of aqueous solution, heating to 92 ℃, adding 1g of titanium tetrachloride, stirring and aging for 2 hours to obtain acid sol;
and step 3: and annealing the steel strip B at 750 ℃ for 60 seconds, aging in a bell-type furnace at 320 ℃ for 8 hours, flattening under 8Mpa to obtain a battery steel strip, and punching to obtain a battery steel shell.
Comparative example 2: the Ni-Fe-Co metal layer is prepared by an electroplating process without magnetron sputtering; otherwise, the same as example 1;
step 1: the surface of a low-carbon steel strip is polished by 600-mesh sand paper, ultrasonically cleaned by acetone for 20 minutes, washed by deionized water, ultrasonically cleaned by 3wt% of sodium hydroxide for 15 minutes, ultrasonically cleaned by 5wt% of sulfuric acid for 15 minutes, washed by deionized water, and placed in Ni-Fe plating solution at the temperature of 45 ℃ and the current density of 4A/dm 2 Electroplating for 200 seconds to obtain a Ni-Fe metal layer which is a steel strip A;
wherein the Ni-Fe plating solution comprises 120g/L nickel sulfate, 30g/L boric acid, 20g/L ferric sulfate, 15g/L lactic acid, 15g/L sodium lactate, 0.2g/L sodium dodecyl sulfate and 0.8g/L saccharin;
and 2, step: placing the steel strip A in a Ni-Fe-Co plating solution at an external magnetic field of 4T and a temperature of 45 ℃ and 4A/dm 2 Electroplating for 50 seconds to obtain a steel strip B;
wherein the components of the Ni-Fe-Co plating solution comprise 100g/L nickel sulfate, 35g/L boric acid, 18g/L ferric sulfate, 12g/L cobalt chloride, 20g/L lactic acid, 15g/L sodium lactate, 0.5g/L sodium dodecyl sulfate and 0.5g/L saccharin;
and step 3: the steel strip B is placed in a Ni-Fe-Co-P bath at a temperature of 50 ℃ and a current density is raised to 5A/dm at a rate of 0.5A/min 2 Electroplating for 720 seconds to obtain a Ni-Fe-Co-P metal layer and obtain a steel strip C;
the Ni-Fe-Co-P plating solution comprises 100g/L of nickel sulfate, 30g/L of boric acid, 18g/L of ferric sulfate, 12g/L of cobalt chloride, 20g/L of nickel chloride, 25g/L of phosphoric acid, 20g/L of lactic acid, 0.1g/L of sodium dodecyl sulfate, 0.012g/L of thiourea, 1.1g/L of acid sol and 0.4g/L of graphene oxide; the preparation of the acidic sol comprises the following steps: dispersing 2g of ammonium ceric nitrate in 30g of aqueous solution, heating to 92 ℃, adding 1g of titanium tetrachloride, stirring and aging for 2 hours to obtain acid sol;
and 4, step 4: and annealing the steel strip C at 750 ℃ for 60 seconds, aging in a bell-type furnace at 320 ℃ for 8 hours, flattening under 8Mpa to obtain a battery steel strip, and punching to obtain a battery steel shell.
Comparative example 3: magnetron sputtering a Ni-Fe-Co metal layer without setting an external magnetic field, and the rest is the same as that of the embodiment 1;
step 1: the surface of a low-carbon steel strip is polished by 600-mesh sand paper, ultrasonically cleaned by acetone for 20 minutes, rinsed by deionized water, ultrasonically cleaned by 3wt% of sodium hydroxide for 15 minutes, ultrasonically cleaned by 5wt% of sulfuric acid for 15 minutes, rinsed by deionized water, and placed in Ni-Fe plating solution at the temperature of 45 ℃ and the current density of 4A/dm 2 Electroplating for 200 seconds to obtain a Ni-Fe metal layer which is a steel strip A;
wherein the Ni-Fe plating solution comprises 120g/L nickel sulfate, 30g/L boric acid, 20g/L ferric sulfate, 15g/L lactic acid, 15g/L sodium lactate, 0.2g/L sodium dodecyl sulfate and 0.8g/L saccharin;
and 2, step: performing magnetron sputtering on the surface of the steel strip A with the sputtering power of 50W and the deposition rate of 0.04nm/s by taking Ni-Fe10at percent to Co10at percent as an alloy target material to obtain a Ni-Fe-Co metal layer with the thickness of 0.15 mu m;
and step 3: placing the steel strip B in Ni-Fe-Co-P plating solution, and increasing the current density to 5A/dm at a rate of 0.5A/min at a temperature of 50 deg.C 2 Electroplating for 720 seconds to obtain a Ni-Fe-Co-P metal layer and obtain a steel strip C;
the Ni-Fe-Co-P plating solution comprises 100g/L of nickel sulfate, 30g/L of boric acid, 18g/L of ferric sulfate, 12g/L of cobalt chloride, 20g/L of nickel chloride, 25g/L of phosphoric acid, 20g/L of lactic acid, 0.1g/L of sodium dodecyl sulfate, 0.012g/L of thiourea, 1.1g/L of acid sol and 0.4g/L of graphene oxide; the preparation of the acidic sol comprises the following steps: dispersing 2g of ammonium ceric nitrate in 30g of aqueous solution, heating to 92 ℃, adding 1g of titanium tetrachloride, stirring and aging for 2 hours to obtain acid sol;
and 4, step 4: and annealing the steel strip C at 750 ℃ for 60 seconds, aging in a bell-type furnace at 320 ℃ for 8 hours, flattening under 8Mpa to obtain a battery steel strip, and punching to obtain a battery steel shell.
Comparative example 4: the Ni-Fe-Co metal layer was increased to 0.3 μm, and the rest was the same as in example 1;
step 1: the surface of a low-carbon steel strip is polished by 600-mesh sand paper, ultrasonically cleaned by acetone for 20 minutes, washed by deionized water, ultrasonically cleaned by 3wt% of sodium hydroxide for 15 minutes, ultrasonically cleaned by 5wt% of sulfuric acid for 15 minutes, washed by deionized water, and placed in Ni-Fe plating solution at the temperature of 45 ℃ and the current density of 4A/dm 2 Electroplating for 200 seconds to obtain a Ni-Fe metal layer which is a steel strip A;
wherein the Ni-Fe plating solution comprises 120g/L nickel sulfate, 30g/L boric acid, 20g/L ferric sulfate, 15g/L lactic acid, 15g/L sodium lactate, 0.2g/L sodium dodecyl sulfate and 0.8g/L saccharin;
step 2: carrying out magnetron sputtering on the surface of the steel strip A by using an external magnetic field of 4T, sputtering power of 50W, deposition rate of 0.04nm/s and Ni-Fe10at% -Co10at% as an alloy target material to obtain a Ni-Fe-Co metal layer with the thickness of 0.3 mu m;
and 3, step 3: placing the steel strip B in a Ni-Fe-Co-P plating solution at a temperature of 50 ℃ and a current densityAt a rate of 0.5A/min to 5A/dm 2 Electroplating for 720 seconds to obtain a Ni-Fe-Co-P metal layer and obtain a steel strip C;
the Ni-Fe-Co-P plating solution comprises 100g/L of nickel sulfate, 30g/L of boric acid, 18g/L of ferric sulfate, 12g/L of cobalt chloride, 20g/L of nickel chloride, 25g/L of phosphoric acid, 20g/L of lactic acid, 0.1g/L of sodium dodecyl sulfate, 0.012g/L of thiourea, 1.1g/L of acid sol and 0.4g/L of graphene oxide; the preparation of the acidic sol comprises the following steps: dispersing 2g of ammonium ceric nitrate in 30g of aqueous solution, heating to 92 ℃, adding 1g of titanium tetrachloride, stirring and aging for 2 hours to obtain acid sol;
and 4, step 4: and (3) annealing the steel strip C at 750 ℃ for 60 seconds, aging in a bell-type furnace at 320 ℃ for 8 hours, flattening under 8Mpa to obtain the battery steel strip, and punching to obtain the battery steel shell.
Comparative example 5: the Ni-Fe-Co-P plating solution is the same as the embodiment 1 except that the acid sol and the graphene oxide are not introduced;
step 1: the surface of a low-carbon steel strip is polished by 600-mesh sand paper, ultrasonically cleaned by acetone for 20 minutes, rinsed by deionized water, ultrasonically cleaned by 3wt% of sodium hydroxide for 15 minutes, ultrasonically cleaned by 5wt% of sulfuric acid for 15 minutes, rinsed by deionized water, and placed in Ni-Fe plating solution at the temperature of 45 ℃ and the current density of 4A/dm 2 Electroplating for 200 seconds to obtain a Ni-Fe metal layer which is a steel strip A;
wherein the Ni-Fe plating solution comprises 120g/L nickel sulfate, 30g/L boric acid, 20g/L ferric sulfate, 15g/L lactic acid, 15g/L sodium lactate, 0.2g/L sodium dodecyl sulfate and 0.8g/L saccharin;
step 2: carrying out magnetron sputtering on the surface of the steel strip A by using an external magnetic field of 4T, sputtering power of 50W, deposition rate of 0.04nm/s and Ni-Fe10at% -Co10at% as an alloy target material to obtain a Ni-Fe-Co metal layer with the thickness of 0.15 mu m;
and step 3: placing the steel strip B in Ni-Fe-Co-P plating solution, and increasing the current density to 5A/dm at a rate of 0.5A/min at a temperature of 50 deg.C 2 Electroplating for 720 seconds to obtain a Ni-Fe-Co-P metal layer and obtain a steel strip C;
wherein the Ni-Fe-Co-P plating solution comprises 100g/L of nickel sulfate, 30g/L of boric acid, 18g/L of ferric sulfate, 12g/L of cobalt chloride, 20g/L of nickel chloride, 25g/L of phosphoric acid, 20g/L of lactic acid, 0.2g/L of sodium dodecyl sulfate, 0.012g/L of thiourea and 0.8g/L of saccharin;
and 4, step 4: and (3) annealing the steel strip C at 750 ℃ for 60 seconds, aging in a bell-type furnace at 320 ℃ for 8 hours, flattening under 8Mpa to obtain the battery steel strip, and punching to obtain the battery steel shell.
Comparative example 6: the Ni-Fe-Co-P bath was used as in example 1, except that the acidic sol was singly introduced.
Step 1: the surface of a low-carbon steel strip is polished by 600-mesh sand paper, ultrasonically cleaned by acetone for 20 minutes, washed by deionized water, ultrasonically cleaned by 3wt% of sodium hydroxide for 15 minutes, ultrasonically cleaned by 5wt% of sulfuric acid for 15 minutes, washed by deionized water, and placed in Ni-Fe plating solution at the temperature of 45 ℃ and the current density of 4A/dm 2 Electroplating for 200 seconds to obtain a Ni-Fe metal layer which is a steel strip A;
wherein the Ni-Fe plating solution comprises 120g/L nickel sulfate, 30g/L boric acid, 20g/L ferric sulfate, 15g/L lactic acid, 15g/L sodium lactate, 0.2g/L sodium dodecyl sulfate and 0.8g/L saccharin;
step 2: performing magnetron sputtering on the surface of the steel strip A by taking Ni-Fe10at% -Co10at% as an alloy target material under the condition of an external magnetic field of 4T and sputtering power of 50W, wherein the deposition rate is 0.04nm/s, so as to obtain a Ni-Fe-Co metal layer with the thickness of 0.15 mu m;
and step 3: the steel strip B is placed in a Ni-Fe-Co-P bath at a temperature of 50 ℃ and a current density is raised to 5A/dm at a rate of 0.5A/min 2 Electroplating for 720 seconds to obtain a Ni-Fe-Co-P metal layer and obtain a steel strip C;
wherein the Ni-Fe-Co-P plating solution comprises 100g/L of nickel sulfate, 30g/L of boric acid, 18g/L of ferric sulfate, 12g/L of cobalt chloride, 20g/L of nickel chloride, 25g/L of phosphoric acid, 20g/L of lactic acid, 0.1g/L of sodium dodecyl sulfate, 0.012g/L of thiourea and 1.5g/L of acid sol; the preparation of the acidic sol comprises the following steps: dispersing 2g of ammonium ceric nitrate in 30g of aqueous solution, heating to 92 ℃, adding 1g of titanium tetrachloride, stirring and aging for 2 hours to obtain acid sol;
and 4, step 4: and annealing the steel strip C at 750 ℃ for 60 seconds, aging in a bell-type furnace at 320 ℃ for 8 hours, flattening under 8Mpa to obtain a battery steel strip, and punching to obtain a battery steel shell.
Comparative example 7: the acid sol only contains a single titanium dioxide, and the rest is the same as the acid sol in the embodiment 1;
step 1: the surface of a low-carbon steel strip is polished by 600-mesh sand paper, ultrasonically cleaned by acetone for 20 minutes, washed by deionized water, ultrasonically cleaned by 3wt% of sodium hydroxide for 15 minutes, ultrasonically cleaned by 5wt% of sulfuric acid for 15 minutes, washed by deionized water, and placed in Ni-Fe plating solution at the temperature of 45 ℃ and the current density of 4A/dm 2 Electroplating for 200 seconds to obtain a Ni-Fe metal layer which is a steel strip A;
wherein the Ni-Fe plating solution comprises 120g/L nickel sulfate, 30g/L boric acid, 20g/L ferric sulfate, 15g/L lactic acid, 15g/L sodium lactate, 0.2g/L sodium dodecyl sulfate and 0.8g/L saccharin;
step 2: carrying out magnetron sputtering on the surface of the steel strip A by using an external magnetic field of 4T, sputtering power of 50W, deposition rate of 0.04nm/s and Ni-Fe10at% -Co10at% as an alloy target material to obtain a Ni-Fe-Co metal layer with the thickness of 0.15 mu m;
and step 3: placing the steel strip B in Ni-Fe-Co-P plating solution, and increasing the current density to 5A/dm at a rate of 0.5A/min at a temperature of 50 deg.C 2 Electroplating for 720 seconds to obtain a Ni-Fe-Co-P metal layer and obtain a steel strip C;
the Ni-Fe-Co-P plating solution comprises 100g/L of nickel sulfate, 30g/L of boric acid, 18g/L of ferric sulfate, 12g/L of cobalt chloride, 20g/L of nickel chloride, 25g/L of phosphoric acid, 20g/L of lactic acid, 0.1g/L of sodium dodecyl sulfate, 0.012g/L of thiourea, 1.1g/L of acid sol and 0.4g/L of graphene oxide; the preparation of the acidic sol comprises the following steps: dispersing 3g of titanium tetrachloride in 30g of aqueous solution, heating to 92 ℃, stirring and aging for 2 hours to obtain acidic sol;
and 4, step 4: and (3) annealing the steel strip C at 750 ℃ for 60 seconds, aging in a bell-type furnace at 320 ℃ for 8 hours, flattening under 8Mpa to obtain the battery steel strip, and punching to obtain the battery steel shell.
And (3) performance testing: the battery steel strips in the examples 1 to 3 and the comparative examples 1 to 7 are characterized by using a tensile testing machine according to a standard method GB/T5027-2016, and the plastic strain ratio is used for characterizing the stamping property; and the steel shell obtained by punching is continuously sprayed with 50g/L sodium chloride solution (the spraying speed is 1.5 mL/h) at 35 ℃ and under the relative humidity of 95 percent . cm 2 Spraying time is 8 hours) Detecting corrosion resistance, and grading according to a standard method GB/T6461-2002; testing the surface hardness according to QB/T3822 by using an HVS-1000 microhardness tester, and testing the microhardness and the overall hardness of the sample by adopting loads of 10g and 200 g; all data are shown in the following table:
results and discussion: as shown by the data in the table, the steel battery shell prepared by the scheme has excellent punching property and corrosion resistance. Comparing the data of the comparative example 1 with the data of the comparative examples 1 to 6 shows that the arrangement of the Ni-Fe-Co metal layer effectively improves the overall hardness and enhances the physical property and the pressure resistance of the steel battery shell while ensuring the stamping property; the data for comparative examples 2 to 4 show that: the Ni-Fe-Co metal layer is plated by an electroplating process, and magnetron sputtering is used due to the difference between crystalline state and thickness control, so that the strengthening performance is higher, the thickness control is accurate, and the integral hardness is improved on the basis of ensuring the stamping performance. In comparative example 3, since the magnetic field was not set, the punching property was lowered; in comparative example 4, the punching property and the overall hardness were reduced due to the increase in the thickness of the magnetron sputtering. On the other hand, in comparative examples 5 to 7, the hardness of the outermost layer was affected by the provision of the metal of the outermost layer, and the wear resistance and scratch resistance were affected thereby; from the comparative example, the performance of the outer layer is reduced and the corrosion resistance is reduced due to the fact that the acid sol and the graphene oxide are not introduced or the acid sol is singly introduced, and the corrosion resistance is reduced due to the fact that the acid sol only contains the single titanium oxide and the rare earth element cerium is introduced.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A processing technology of a battery steel shell with a metal layer plated on the surface is characterized by comprising the following steps: the method comprises the following steps:
step 1: polishing the surface of the low-carbon steel strip, performing alkali washing, acid washing and water washing, placing the low-carbon steel strip in a Ni-Fe plating solution, and electroplating to obtain a Ni-Fe metal layer which is a steel strip A;
step 2: performing magnetron sputtering on the surface of the steel strip A to obtain Ni-Fe-Co, wherein the alloy target is Ni-Fe10at% -Co10at%, and the technological parameters are as follows: 2 to 5T of external magnetic field, 30 to 50W of sputtering power and 0.03 to 0.05nm/s of deposition rate; obtaining a Ni-Fe-Co metal layer which is a steel strip B;
and 3, step 3: placing the steel strip B in a Ni-Fe-Co-P plating solution, and electroplating to obtain a Ni-Fe-Co-P metal layer to obtain a steel strip C;
and 4, step 4: and annealing, aging and flattening the steel strip C to obtain a battery steel strip, and punching to obtain a battery steel shell.
2. The process for manufacturing a steel battery case plated with a metal layer on the surface according to claim 1, wherein the metal layer is formed by: the thickness of the Ni-Fe metal layer is 0.6 to 1 mu m; the thickness of the Ni-Fe-Co metal layer is 0.12 to 0.17 mu m; the thickness of the Ni-Fe-Co-P metal layer is 2.5 to 3.5 mu m.
3. The process according to claim 1, wherein the metal layer is plated on the surface of the steel battery shell, and the process comprises the following steps: in step 1, the components of the Ni-Fe plating solution comprise the following substances: 100-120g/L of nickel sulfate, 30-40g/L of boric acid, 20-30g/L of ferric sulfate, 10-20g/L of lactic acid, 10-20g/L of sodium lactate, 0.1-0.2g/L of sodium dodecyl sulfate and 0.8-0.9g/L of saccharin; the electroplating process parameters of the Ni-Fe metal layer are as follows: the temperature is 40 to 50 ℃, and the current density is 3 to 4A/dm 2 The plating time was 160 to 240 seconds.
4. The process for manufacturing a steel battery case plated with a metal layer on the surface according to claim 1, wherein the metal layer is formed by: in step 3, the Ni-Fe-Co-P plating solution comprises the following components: 100-120g/L of nickel sulfate, 30-35g/L of boric acid, 18-20g/L of ferric sulfate, 10-12g/L of cobalt chloride, 20-25g/L of nickel chloride, 20-30g/L of phosphoric acid, 10-20g/L of lactic acid, 0.1-0.2g/L of sodium dodecyl sulfate, 0.01-0.015g/L of thiourea, 1-1.2g of acidic sol and 0.3-0.5g/L of graphene oxide.
5. The process for manufacturing a steel battery case plated with a metal layer on the surface according to claim 4, the method is characterized in that: the acid sol is a mixed sol of titanium dioxide and cerium dioxide; the method specifically comprises the following steps: dispersing ammonium ceric nitrate in an aqueous solution, heating to 90-95 ℃, adding titanium tetrachloride, stirring and aging for 2 hours to obtain acidic sol; the mass ratio of the ammonium ceric nitrate to the titanium tetrachloride is (1.5-2) 1.
6. The process according to claim 1, wherein the metal layer is plated on the surface of the steel battery shell, and the process comprises the following steps: in step 3, the electroplating process parameters of the Ni-Fe-Co-P metal layer are as follows: the temperature is 45 to 55 ℃, and the current density is increased to 4 to 6A/dm at the speed of 0.5A/min 2 The total plating time is 600 to 840 seconds.
7. The process for manufacturing a steel battery case plated with a metal layer on the surface according to claim 1, wherein the metal layer is formed by: in the step 4, the annealing temperature is 700 to 780 ℃, and the time is 60 to 90 seconds; the aging temperature is 300 to 350 ℃, the time is 6 to 10 hours, and the leveling pressure is 6 to 8Mpa.
8. The steel battery shell prepared by the processing technology of the steel battery shell with the metal layer plated on the surface according to any one of claims 1 to 7.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101958404A (en) * | 2010-02-10 | 2011-01-26 | 湘潭大学 | Nanowire-containing multilayer composite thin film plated steel belt and preparation method thereof |
| CN102876971A (en) * | 2012-09-24 | 2013-01-16 | 无锡市方正金属捆带有限公司 | Method for manufacturing nickel-chromium plating steel band for battery steel shell |
| CN105463540A (en) * | 2015-11-26 | 2016-04-06 | 湖南永盛新材料股份有限公司 | Nickel-cobalt/nickel/nickel-phosphorus multi-layer film plated stainless steel strip and manufacturing method thereof |
| US20210269929A1 (en) * | 2018-07-06 | 2021-09-02 | Nippon Steel Corporation | Surface-treated steel sheet and method for manufacturing surface-treated steel sheet |
| CN114540604A (en) * | 2022-02-23 | 2022-05-27 | 江苏东方九天新能源材料有限公司 | Nickel-plated steel strip for battery container and preparation method thereof |
| CN115323373A (en) * | 2022-08-15 | 2022-11-11 | 苏州中成同人新材料科技有限公司 | Wear-resistant aluminum alloy for automobile heat exchanger and preparation method thereof |
-
2023
- 2023-02-06 CN CN202310065747.4A patent/CN115786913B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101958404A (en) * | 2010-02-10 | 2011-01-26 | 湘潭大学 | Nanowire-containing multilayer composite thin film plated steel belt and preparation method thereof |
| CN102876971A (en) * | 2012-09-24 | 2013-01-16 | 无锡市方正金属捆带有限公司 | Method for manufacturing nickel-chromium plating steel band for battery steel shell |
| CN105463540A (en) * | 2015-11-26 | 2016-04-06 | 湖南永盛新材料股份有限公司 | Nickel-cobalt/nickel/nickel-phosphorus multi-layer film plated stainless steel strip and manufacturing method thereof |
| US20210269929A1 (en) * | 2018-07-06 | 2021-09-02 | Nippon Steel Corporation | Surface-treated steel sheet and method for manufacturing surface-treated steel sheet |
| CN114540604A (en) * | 2022-02-23 | 2022-05-27 | 江苏东方九天新能源材料有限公司 | Nickel-plated steel strip for battery container and preparation method thereof |
| CN115323373A (en) * | 2022-08-15 | 2022-11-11 | 苏州中成同人新材料科技有限公司 | Wear-resistant aluminum alloy for automobile heat exchanger and preparation method thereof |
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