CN101954763B - Nickeliferous nanowire laminated film plated steel belt and production method thereof - Google Patents
Nickeliferous nanowire laminated film plated steel belt and production method thereof Download PDFInfo
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- CN101954763B CN101954763B CN201010110136XA CN201010110136A CN101954763B CN 101954763 B CN101954763 B CN 101954763B CN 201010110136X A CN201010110136X A CN 201010110136XA CN 201010110136 A CN201010110136 A CN 201010110136A CN 101954763 B CN101954763 B CN 101954763B
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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
Abstract
The invention discloses a nickeliferous nanowire laminated film plated steel belt and a production method thereof. A steel belt is used as a base, and both faces of the steel belt are respectively plated with a nickeliferous nanowire multilayer laminated film. The bottom layer of the nickeliferous nanowire multilayer laminated film is a micron-crystalline nickel plating layer, the middle layer is a nickeliferous nanowire nickel laminated plating layer, and the surface layer is a micron-crystalline nickel cobalt alloy plating layer. The invention also provides the production method of the steel belt, which comprises the following steps of: oiling and activating the base steel belt, and firstly preparing one micron-crystalline nickel plating layer on the base by using a DC electroplating mode; after annealing, preparing one nickeliferous nanowire nickel laminated plating layer on the nickel plating layer by using a pulse electroplating mode; then, preparing one micron-crystalline nickel cobalt alloy plating layer on the nickeliferous nanowire nickel laminated plating layer by using a pulse spraying mode, cleaning by using distilled water and drying; and finally, preserving temperature and removing hydrogen. The steel belt is formed by tightly combining the nickeliferous nanowire multilayer laminated film and a mild-carbon steel belt together, has good corrosion resistance, stamping performance and strong load resistance and can be applied to shell materials of lithium ion power batteries and high-performance alkaline manganese batteries.
Description
Technical field
The present invention relates to a kind of plating steel band of nickeliferous nano wire laminated film and preparation method thereof is arranged.
Background technology
Along with becoming increasingly conspicuous of the problems such as environmental pollution, energy crisis and shortage of resources, the development of the correlation technique such as countries in the world are more and more paid much attention to efficiently, cleaning, regenerative resource and electric automobile, electric bicycle, portable power tool.Lithium ion battery is the novel green energy storage device that development in recent years is got up, lithium ion battery has caused people's extensive concern because of its high-energy-density and high-rate discharge ability, not only be used widely at portable electric appts, and being applied to gradually the big-and-middle-sized electrical equipment aspects such as electric automobile, electric bicycle and electric tool, lithium-ion-power cell especially wherein is the main direction of present each macrocell producer development.
The bump that electric automobile may run in the process of moving, jolt and at a high speed brake cause the situations complicated and changeable such as strong concussion, the security performance of battery under severe service condition had higher requirement, and the security performance of lithium-ion-power cell has also become the bottleneck place of Development of Electric Vehicles.For this reason, expert both domestic and external has carried out a large amount of research to lithium-ion-power cell in all its bearings, seeks to solve the security of lithium-ion-power cell problem.
Shell as lithium-ion-power cell not only will have good electrolyte resistance corrosive nature, and storge quality and the security performance of battery had very important effect.When the bump that runs into, jolt and when at a high speed brake caused the situation complicated and changeable such as strong concussion, box hat will bear Strong Impact Loading in short-term.So box hat plays larger effect to the security performance of lithium ion battery.
Chinese patent CN100426558C discloses a kind of preparation method who can be used as the battery steel shell of lithium ion battery.Its principal character is to form ferro-nickel alloy plating at steel plate, and after the punch forming, the coating of box hat sidewall and bottom has certain proportion requirement, satisfies battery steel shell to the requirement of decay resistance.
US Patent No. 4760002 disclose a kind of on mild-carbon steel strip first plating one deck nickel film, and then plating one deck cobalt thin film forms steel band and the production method of nickel cobalt or permivar again through heat diffusion treatment.
Yet said method lays particular emphasis on the Anticorrosion Problems that solves battery container, and does not consider the anti-strong load demand as the power lithium-ion battery shell.
At Nano Letters 2007,7 (5): mention in the people such as D.X.Wang shows among the 1208-1212 " Where; and how; does a nanowire break ", after most of metal material becomes the very large microcosmic nano wire of draw ratio from macro-size, the variation of mechanical property generation highly significant makes nano wire have better plasticity and ductility.
At Physical Review Letters1999,82:2900-2903.Hideyuki Ikeda mentions among " the Strainrate induced amorphization in metallic nanowires " that waits the people to show, such as under the nickel nano wire room temperature at 5%ps
-1Strain rate under when being out of shape, its elasticity can reach 7.5%, yield stress can reach 5.5GPa, is higher than the block nickel material far away.When deformation occured, dislocation and the relaxation process of nickel nanometer hocketed, and make it to have very strong ductility or plasticity.
Chinese patent CN101311330C discloses a kind of nickel composite film that is formed by one dimension nickel nano wire and two-dimentional nickel Film laminated and preparation method thereof.This nickel composite film has good mechanical property and processing characteristics, can resist larger shock loading, and have with low cost, the simple advantage of technique.But directly plating one deck compound nickel film of containing nano wire has two large shortcomings on steel band, and the adhesion of the first and substrate is relatively poor, and it two is that case hardness is lower, scratches easily during punching press.
Summary of the invention
Technical problem to be solved by this invention provides a kind of plating steel band of nickeliferous nano wire laminated film and preparation method thereof.This steel band is combined closely by the multi-layer compound film of nickeliferous nano wire and mild-carbon steel strip and is formed, and has good decay resistance, punching performance and anti-strong load-carrying ability.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is:
A kind of plating has the steel band of nickeliferous nano wire laminated film, it is characterized in that, take mild-carbon steel strip as substrate (1), described mild-carbon steel strip is the BDCK battery special steel strip that Shanghai Baoshan Steel stock Co., Ltd produces, and the multilayer film of nickeliferous nano wire is arranged at steel band two sides plating.The bottom of multilayer film is micron brilliant nickel coating (2), and crystallite dimension is that 0.1～0.5 μ m, thickness are 0.5～2 μ m; The intermediate layer is the nickel composite deposite (3) of nickeliferous nano wire, and crystallite dimension is that 50～100nm, thickness are 0.5～1.5 μ m; The top layer is nanocrystalline nickel-cobalt alloy plating (4), and crystallite dimension is that 20～50nm, thickness are 0.1～0.5 μ m.
The content of nickel nano wire is 0.5wt%～5wt% in the nickel composite deposite of described nickeliferous nano wire, and the diameter of nickel nano wire is 20～40nm, and length is 0.5～1 μ m.Described nickel nano wire is prepared from by anodic oxidation aluminium formwork electro-deposition (AAO).
The cobalt content of described nanocrystalline nickel-cobalt alloy plating is 0.5～5wt%.
Plating as battery case of the present invention has the manufacturing approach craft step of steel band of multi-layer compound film of nickeliferous nano wire as follows:
1, mild-carbon steel strip is plated pre-treatment:
In order to make coating and substrate that good combination be arranged, must the target substrate carry out surface preparation before electroplating.Because the surface of used mild-carbon steel strip is more smooth, do not need polishing and machine glazed finish before the nickel plating, directly carry out oil removal treatment.Adopt chemical high temperature deoiling method, degreasing fluid is the NaOH of 70g/L, the Na of 40g/L
2CO
3, 25g/L Na
3PO
4, 10g/L Na
2SiO
3Mixed solution.Mild-carbon steel strip is immersed in except being heated to 80～90 ℃ in the oil solution, takes out behind 3～5min, observe the surface during washing and whether stop droplet, if any then continuing oil removing.After the oil removing fully, with distilled water specimen surface is rinsed well, then put into 1～5vol%HCl activation, 0.5～2min, for electroplating reaction provides active surface.The taking-up sample is electroplated after again cleaning with distilled water immediately.
2, dc source is electroplated the brilliant nickel dam bottom of micron:
Plating bath forms:
Seven water and nickelous sulfate NiSO
47H
2O 250～300g/L
Six water and nickel chloride NiCl
26H
2O 30～50g/L
Boric acid H
3BO
330～50g/L
The direct current electrode position technological parameter:
Current density: 3～6A/dm
2
PH value: 3.5～4.5
Anode: nickel plate
Temperature: 40～60 ℃
3, will electroplate the brilliant nickel coating of micron steel band afterwards places box-annealing furnace at protective atmosphere (25%N
2+ 75%H
2) lower annealing in process.200 ℃～750 ℃ of annealing temperatures, annealing time 2～6h.The purpose of annealing in process is to form the Ni-Fe diffusion layer between mild steel and the brilliant nickel coating of micron, strengthens the adhesion between coating and the substrate.
4, be mixed with the nickel composite deposite of nickel nano wire with the method preparation of pulse plating on the two sides of steel band.The concrete technology parameter is as follows:
The nickel composite film plating bath that contains suspension nickel nano wire forms:
NiSO
4·7H
2O 200～300g/L
NiCl
2·6H
2O 40～60g/L
H
3BO
3 30～40g/L
Saccharin sodium 1.0～1.5g/L
Nickel nano wire 1～5g/L
Softex kw 1.4～4.2 * 10
-3Mol (g nickel nano wire)
-1
The pulse plating process parameter:
Average current density 3～5A/dm
2
i
on 5～50ms
i
off 5～250ms
40～70 ℃ of temperature
PH value 3.5～5.5
Ultrasonic wave stirring frequency 40～60Hz
Ultrasonic wave power of agitator 200～400W
Anode nickel plates
5, adopt the impulse jet electric plating method to prepare nanocrystalline nickel-cobalt alloy plating on the two sides of steel band.Its concrete technology parameter is as follows:
Plating bath forms: seven water and nickelous sulfate NiSO
47H
2O 180～220g/L
Six water and nickel chloride NiCl
26H
2O 40～60g/L
Cobaltous sulfate CoSO
47H
2O 10～15g/L
Boric acid H
3BO
325～35g/L
ALS 0.4～2g/L
Butynediols 0.4～0.5ml/L
Asccharin 0.8～1.0g/L
Impulse jet electroplating technological parameter: peak current density: 47～82A/dm
2
Dutycycle: 15～25%
Plating bath spray speed: 1000～1500L/h
Temperature: 55～65 ℃
PH value: 2.5～3.5
Anode: nickel cobalt (alloy) pipe
6, it is clean with distilled water flushing to plate good steel band, then oven dry.
7, will plate good steel band and place and be incubated under 150～200 ℃ of conditions, to remove the hydrogen that in electroplating process, produces in the coating.
Beneficial effect:
The present invention considers that from multi-layer film material design synthesis advantage annealed processing after the brilliant nickel coating of plated underlayer one deck micron is in order to improve the adhesion of multilayer coating and substrate; Plating contains the nickel composite deposite of nano wire again, plates the nanocrystalline nickel-cobalt alloy plating of one deck in the outside that contains the nano wire laminated film again, is used for improving coating surface hardness, avoids scratching in punching course steel strip surface.
Plating as the power lithium-ion battery shell of the present invention has the steel band of the multi-layer compound film of nickeliferous nano wire, adopted multi-layer film structure, have higher intensity and case hardness, can improve the bond strength of substrate and coating, reduce the space in the coating, can improve the thin layer internal stress and distribute.Because the inventor has carried out effectively limiting to the thickness of the film of each layer and the crystallite dimension of formation film, so that material of the present invention is demonstrating the peculiar character that obviously is different from the conventional monolayers material aspect the decay resistance of mechanics, electricity, magnetics and material.On the one hand, when the crystal grain that forms film is little during to Nano grade, the defectives such as crystal boundary and dislocation can increase, and the nucleating center of passivating film will increase, thereby cause film surface that more passivating film is arranged; On the other hand, when the crystal grain that forms film is little during to nanoscale, the diffusion rate of ion can be higher, easier formation passivation layer, thus reduced the corrosion rate of film, and then make steel band have good decay resistance.Compound nickel nano wire can form more crystal boundary in the nano-crystal nickel film, therefore, in multilayer film, adopts the Ni-based laminated film of nickeliferous nano wire, can obviously improve the decay resistance of battery container.
Generally, along with reducing of size, nano wire can embody than the better mechanical property of massive material, is mainly manifested in elasticity and plasticity and all greatly improves.Compound nickel nano wire in the nickel coating of MULTILAYER COMPOSITE coating, can be implemented in the situation that does not reduce coating surface hardness and improve ductility of electrodeposited film, improve coating punching performance, surface scratch resistance energy and anti-strong load performance, thereby improve the security performance of power lithium-ion battery when the strong load such as being clashed into.
The plating that the inventive method makes has the steel band of nickeliferous nano wire laminated film when having good percentage elongation and corrosion resistance, have good case hardness and ductility of electrodeposited film, be beneficial to punch forming, can be used as the case material of lithium-ion-power cell and other heavy-duty batteries.
Steel band of the present invention adopts the BDCK battery special steel strip of Shanghai Baoshan Steel stock Co., Ltd production as substrate (1), the bottom of multi-layer compound film is the brilliant nickel coating (2) of micron, the intermediate layer is the nickel composite deposite (3) of nickeliferous nano wire, and outermost layer is nanocrystalline nickel-cobalt alloy plating (4).As shown in Figure 1.
The brilliant nickel coating of micron of bottom after annealing in process, can form good combination by the technique preparation of direct current electrode position with substrate, prevents that coating from coming off.Its crystallite dimension is 0.2～0.5 μ m, and elite 0.5～2 μ m of thickness because in the situation of thickness less than 0.5 μ m, can not reach the corrosion-resistant effect well.In addition, nickel coating can surpass 2 μ m, but the blocked up meeting of coating causes the increase of cost.
The nickel composite deposite of the nickeliferous nano wire in intermediate layer is that the nickel nano wire with finite concentration (15g/L) joins in the nickel plating solution that configures, and prepares by the normal pulsed electric plating method.Because the nickel nano wire has good mechanical property, the nickel composite deposite of nickeliferous nano wire can significantly increase the obdurability of multilayer film coating when not reducing multi-layer film surface hardness, increases the anti-strong load-carrying ability of battery container.Preferred 0.1～0.5 μ m of intermediate layer thickness.
The nanocrystalline nickel-cobalt alloy plating on top layer has higher hardness by the preparation of impulse jet electroplating technique, and its crystallite dimension is 20～50nm, and thickness is 0.1～0.5 μ m.Nanocrystalline nickel-cobalt alloy plating has surfacing, densification, porosity is low, crystal grain is tiny, hardness is high, the electrical conductivity high.Because the nanocrystalline nickel-cobalt alloy plating in top layer has the passivating film nucleating point of higher density, thereby so that nanocrystalline coating has high-quality passivating film and lower corrosion rate, be applied in the inner surface of battery container, can obviously improve decay resistance and the electric property of battery container; Be applied to the outer surface of battery container, owing to its surfacing, hardness height, can reduce the surface tear in the punching course, reduce coefficient of friction, more be conducive to the streamline production of battery container, enhance productivity.
Description of drawings
Fig. 1 is the structural representation of steel band of the present invention, and wherein 1 is substrate (mild-carbon steel strip); 2 is the brilliant nickel coating of micron; 3 is nickel composite deposite; 4 is nanocrystalline nickel-cobalt alloy plating; Nickel composite deposite is the MULTI-LAYER NICKEL composite deposite of nickeliferous nano wire.
Fig. 2 is process chart of the present invention.
The specific embodiment
The invention will be further described below in conjunction with accompanying drawing.
Embodiment 1
The thickness of selecting Shanghai Baoshan Steel stock Co., Ltd to produce is that the BDCK battery special steel strip of 0.25mm is as substrate.Its chemical composition is: C:0.029% (% represents percetage by weight, and is lower same)
Si：0.02％
Mn：0.2％
P：0.09％
S：0.003％
Al：0.06％。
(preliminary treatment of plating front surface)
In order to make coating and substrate form good combination, before plating, above-mentioned steel band is carried out following surface preparation.Because the surface of used mild-carbon steel strip is more smooth, do not need polishing and machine glazed finish before the nickel plating, directly carry out oil removing and activation process.This example adopts chemical high temperature deoiling method.
Degreasing fluid forms:
NaOH 70g/L
Na
2CO
3 40g/L
Na
3PO
4 25g/L
Na
2SiO
3 10g/L
Degreasing fluid temperature: 80 ℃
The oil removing time: 3min
After the oil removing fully, with distilled water specimen surface is rinsed well, then put into activator and activate.
Activator forms: 3vol%HCl
Soak time: 1min
(the brilliant nickel coating of direct current electrode position micron)
Plating bath forms:
Seven water and nickelous sulfate NiSO
47H
2O 280g/L
Six water and nickel chloride NiCl
26H
2O 40g/L
Boric acid H
3BO
340g/L
The direct current electrode position technological parameter:
Current density: 4A/dm
2
PH value: 4
Anode: nickel plate
Temperature: 50 ℃
Time: 60s
(annealing in process)
Under these conditions, preparing one deck crystallite dimension is 0.1～0.5 μ m, and thickness is the brilliant nickel coating of micron of 0.8 μ m.
Place box-annealing furnace at protective atmosphere (25%N with electroplating the brilliant nickel coating of micron steel band afterwards
2+ 75%H
2) lower annealing in process.650 ℃ of annealing temperatures, annealing time 4h.
(pulse plating is mixed with the nickel composite deposite of nickel nano wire)
A kind of preparation technology of nickel cobalt laminated film of nickeliferous nano wire comprises following processing step (such as Fig. 2):
(1) preparation of the nickel cobalt laminated film plating bath of nickeliferous nano wire: take by weighing a certain amount of NiSO
47H
2O and NiCl
26H
2O is dissolved in the deionized water, through magnetic agitation and appropriate heating, mixture is dissolved fully, obtains solution A; Take by weighing a certain amount of H
3BO
3Put into another container, then add a small amount of deionized water, through magnetic agitation and appropriate heating, obtain the solution B of transparent clarification; Solution B is added solution A, add again a certain amount of saccharin sodium, magnetic agitation 20min, and then add a certain amount of nickel nano wire and a certain amount of softex kw (CTAB), after stirring 30min, ultrasonic wave obtains containing the nickel composite film plating bath of suspension nickel nano wire.
(2) preparation of the nickel cobalt laminated film of nickeliferous nano wire: (1) the nickel cobalt laminated film plating bath that contains suspension nickel nano wire that obtains of step put into be with hyperacoustic water bath with thermostatic control (50 ℃ of thermostat temperatures), and carry out ultrasonic agitation, then there is plating the steel band of the brilliant nickel of micron to put into the laminated film plating bath, the negative pole that connects power supply, positive pole connects the nickel plate, carries out composite plating.
The nickel cobalt laminated film plating bath that contains suspension nickel nano wire forms:
NiSO
4·7H
2O 250g/L
NiCl
2·6H
2O 50g/L
H
3BO
3 35g/L
Saccharin sodium 1.2g/L
Nickel nano wire 3g/L
Softex kw 4.2 * 10
-3Mol
The pulse plating process parameter:
Average current density 4A/dm
2
i
on 30ms
i
off 120ms
Temperature 60 C
PH value 4.5
Ultrasonic wave stirring frequency 50Hz
Ultrasonic wave power of agitator 300W
Anode nickel plates
Time: 60s
Under these conditions, preparing one deck crystallite dimension is 50～100nm, and thickness is the nickel cobalt laminated film coating of the suspension nickel nano wire of 0.8 μ m.
(impulse jet nickel-cobalt alloy plating coating)
Plating bath forms: seven water and nickelous sulfate NiSO
47H
2O 200g/L
Six water and nickel chloride NiCl
26H
2O 50g/L
Cobaltous sulfate CoSO
47H
2O 12g/L
Boric acid H
3BO
330g/L
ALS 1.2g/L
Butynediols 0.5ml/L
Asccharin 0.8g/L
Impulse jet electroplating technological parameter: peak current density: 65A/dm
2
Dutycycle: 20%
Plating bath spray speed: 1400L/h
Temperature: 60 ℃
PH value: 3
Anode: nickel cobalt (alloy) pipe
Time: 10s
(washing, oven dry)
Under these conditions, preparing one deck crystallite dimension is 20～50nm, and thickness is the nickel-cobalt alloy plating of 0.5 μ m.
The steel band that plating is good is clean with distilled water flushing, then oven dry.
(insulation dehydrogenation)
The steel band that plating is good places 200 ℃ of lower insulations, to remove the hydrogen that produces in the coating in electroplating process.The nickel cobalt laminated film of the nickeliferous nano wire that makes as shown in Figure 1.
Performance test
Produce in the following manner sample, as a comparative example.
Comparative example preparation method: select the substrate identical with embodiment and plating pre-treating method.Adopt the method for direct current electrode position, equal plating a layer thickness is the brilliant nickel coating of micron of 2.2 μ m on the substrate two sides, and electroplating technology is as follows:
Plating bath comprises: seven water and nickelous sulfate NiSO
47H
2O 280g/L
Six water and nickel chloride NiCl
26H
2O 40g/L
Boric acid H
3BO
340g/L
Direct current electrode position technological parameter: current density: 4A/dm
2
PH value: 4
Anode: nickel plate
Electroplating time: 160s
With the obtained material of comparative example at protective atmosphere (25%N
2+ 75%H
2) under do the insulation dehydrogenation, temperature is 200 ℃, temperature retention time 3 hours.At last the gained steel band is annealed and cold-rolling treatment.
The material that embodiment and comparative example are made carries out neutral salt spray test.Table 1 is the neutral salt spray test comparing result.
Table 1 neutral salt spray test tables of data
| 4 hours | 8 hours | 12 hours | 16 hours | 20 hours | 24 hours | |
| Embodiment | Without rust spot | 1 rust spot | 2 rust spots | 4 rust spots | 8 rust spots | 12 rust spots, rust spot become large |
| BDCK | 1 rust spot | 2 rust spots | 5 rust spots | 13 rust spots | 31 rust spots, rust spot become large | Heavy corrosion |
Claims (5)
1. a plating has the steel band of nickeliferous nano wire laminated film, it is characterized in that take mild-carbon steel strip as substrate, the multilayer film of nickeliferous nano wire being arranged at steel band two sides plating; The bottom of multilayer film is the brilliant nickel coating of micron, and crystallite dimension is that 0.1～0.5 μ m, thickness are 0.5～2 μ m; The intermediate layer is the nickel composite deposite of nickeliferous nano wire, and crystallite dimension is that 50～100nm, thickness are 0.5～1.5 μ m; The top layer is nanocrystalline nickel-cobalt alloy plating, and crystallite dimension is that 20～50nm, thickness are 0.1～0.5 μ m;
Bottom micron crystalline substance prepares by the direct current electrode position mode in this coating, and the nickel composite deposite of the nickeliferous nano wire in intermediate layer obtains by pulse plating, and the nanocrystalline of top layer is to obtain by the mode that impulse jet is electroplated.
2. plating according to claim 1 has the steel band of nickeliferous nano wire laminated film, it is characterized in that, the content of nickel nano wire is 0.5～5wt% in the nickel composite deposite of described nickeliferous nano wire, the diameter of nickel nano wire is 20～40nm, length is 0.5～1 μ m, and described nickel nano wire is prepared from by the anodic oxidation aluminium formwork electro-deposition.
3. plating according to claim 1 has the steel band of nickeliferous nano wire laminated film, it is characterized in that, the cobalt content of described nanocrystalline nickel-cobalt alloy plating is 0.5～5wt%.
4. plating claimed in claim 1 has the preparation method of the steel band of nickeliferous nano wire laminated film, it is characterized in that, may further comprise the steps:
1) substrate surface preliminary treatment before the plating;
2) at the brilliant nickel coating of the two sides of substrate direct current electrode position micron:
The plating bath of direct current electrode position forms:
Seven water and nickelous sulfate NiSO
47H
2O 250～300g/L;
Six water and nickel chloride NiCl
26H
2O 30～50g/L;
Boric acid H
3BO
330～50g/L;
The direct current electrode position technological parameter:
Current density: 3～6A/dm
2
PH value: 3.5～4.5;
Anode: nickel plate;
Temperature: 40～60 ℃;
3) annealing in process: will electroplate the brilliant nickel coating of micron steel band annealing in process under protective atmosphere afterwards, annealing temperature is 200 ℃～750 ℃, annealing time 2～6h;
4) method of pulse plating is adopted on the two sides of the steel band after annealing in process, and preparation is mixed with the nickel composite deposite of nickel nano wire;
Specifically may further comprise the steps:
(1) preparation of the nickel composite film plating bath of nickeliferous nano wire: with NiSO
47H
2O and NiCl
26H
2O is dissolved in the deionized water, stirs, so that solids dissolves fully, obtains solution A; With H
3BO
3Put into another container, then add deionized water, stir, obtain the solution B of transparent clarification; Solution B is added solution A, add again saccharin sodium, stir 20min, and then adding is 20～40nm by the standby diameter that forms of alumina formwork legal system, length is nickel nano wire and the softex kw of 0.5～1 μ m, obtain containing the nickel composite film plating bath of suspension nickel nano wire after ultrasonic wave stirs 30min, plating bath is composed as follows:
(2) preparation of the nickel composite film of nickeliferous nano wire: the nickel composite film plating bath that contains suspension nickel nano wire that step (1) is obtained is put into and is with hyperacoustic water bath with thermostatic control, 50 ℃ of thermostat temperatures, and carry out ultrasonic agitation, then there is plating the steel band of the brilliant nickel of micron to put into the laminated film plating bath of step (1), the negative pole that connects power supply, positive pole connects the nickel plate, carries out composite plating;
The pulse plating process parameter:
5) at the two sides of steel band impulse jet nickel-cobalt alloy plating coating:
The plating bath of impulse jet forms: seven water and nickelous sulfate NiSO
47H
2O 180～220g/L;
Six water and nickel chloride NiCl
26H
2O 40～60g/L;
Cobaltous sulfate CoSO
47H
2O 10～15g/L;
Boric acid H
3BO
325～35g/L;
ALS 0.4～2g/L;
Butynediols 0.4～0.5ml/L;
Asccharin 0.8～1.0g/L;
Impulse jet electroplating technological parameter: peak current density: 47～82A/dm
2
Dutycycle: 15～25%;
Plating bath spray speed: 1000～1500L/h
Temperature: 55～65 ℃;
PH value: 2.5～3.5;
Anode: nickel cobalt (alloy) pipe;
6) steel band with gained is clean with distilled water flushing, and then oven dry places under 150～200 ℃ of conditions again and is incubated dehydrogenation.
5. plating according to claim 4 has the preparation method of the steel band of nickeliferous nano wire laminated film, it is characterized in that, the substrate surface preliminary treatment is carried out chemical high temperature oil removing for first degreasing fluid being put in substrate before the described plating of step 1); Then rinse well with the substrate surface of distilled water after with oil removing, put into activator and activate.
Degreasing fluid is: NaOH 70g/L
Na
2CO
3 40g/L
Na
3PO
4 25g/L
Na
2SiO
3 10g/L
Degreasing fluid temperature: 80～90 ℃
The oil removing time: 3～5min
After the oil removing fully, with distilled water specimen surface is rinsed well, then put into activator and activate;
Activator is: 1～5vol%HCl
Soak time: 0.5～2min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010110136XA CN101954763B (en) | 2010-02-10 | 2010-02-10 | Nickeliferous nanowire laminated film plated steel belt and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010110136XA CN101954763B (en) | 2010-02-10 | 2010-02-10 | Nickeliferous nanowire laminated film plated steel belt and production method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101954763A CN101954763A (en) | 2011-01-26 |
| CN101954763B true CN101954763B (en) | 2013-03-13 |
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| CN103343367A (en) * | 2013-07-12 | 2013-10-09 | 深圳市中金高能电池材料有限公司 | Nickel-plated steel strip and preparation method thereof |
| CN104164685B (en) * | 2014-06-11 | 2018-10-12 | 安徽长青电子机械（集团）有限公司 | A kind of method of steel plate nickel plating |
| CN105063677A (en) * | 2015-08-21 | 2015-11-18 | 无锡桥阳机械制造有限公司 | Electroplating nickel solution and electroplating method thereof |
| CN105177650A (en) * | 2015-09-10 | 2015-12-23 | 湖南东洋利德材料科技有限公司 | Nickel plating method of steel belts for steel battery shells |
| CN105196646A (en) * | 2015-09-16 | 2015-12-30 | 无锡朗盛线缆材料有限公司 | Composite film for steel aluminum plastic strip |
| CN106245069A (en) * | 2015-12-01 | 2016-12-21 | 江苏九天光电科技有限公司 | A kind of preparation method of the quick electronickelling steel band for battery case |
| WO2018015168A1 (en) * | 2016-07-18 | 2018-01-25 | Basf Se | Composition for cobalt plating comprising additive for void-free submicron feature filling |
| CN109301094A (en) * | 2017-07-25 | 2019-02-01 | 宁波堇山新材料有限公司 | A kind of plating Ni steel band uses the preparation method of the battery steel shell of the steel band and the steel shell |
| CN115787014B (en) * | 2022-11-30 | 2023-10-13 | 江苏东方九天新能源材料有限公司 | Surface treatment process of nickel-plated steel strip of battery |
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| CN201289867Y (en) * | 2008-10-27 | 2009-08-12 | 株洲永盛电池材料有限公司 | Single side nickel-clad stainless steel band for fastening lithium ion cell case and cover |
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| CN201619267U (en) * | 2010-02-10 | 2010-11-03 | 湘潭大学 | Steel strip coated with composite films containing nickel nanowires |
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| JP2006093096A (en) * | 2004-08-23 | 2006-04-06 | Toyo Kohan Co Ltd | Plated steel sheet for battery container, battery container using same, and battery using its battery container |
| WO2007091732A2 (en) * | 2006-02-09 | 2007-08-16 | Nippon Steel Corporation | Tinned steel sheet excellent in corrosion resistance |
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| CN201289867Y (en) * | 2008-10-27 | 2009-08-12 | 株洲永盛电池材料有限公司 | Single side nickel-clad stainless steel band for fastening lithium ion cell case and cover |
| CN101597780A (en) * | 2009-07-03 | 2009-12-09 | 湖南利德材料科技股份有限公司 | A kind of method for preparing the nickel-silver alloy steel strip that battery case uses |
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