CN101954762A - Steel strip plated with composite film containing cobalt nanowires and preparation method thereof - Google Patents
Steel strip plated with composite film containing cobalt nanowires and preparation method thereof Download PDFInfo
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- CN101954762A CN101954762A CN2010101101266A CN201010110126A CN101954762A CN 101954762 A CN101954762 A CN 101954762A CN 2010101101266 A CN2010101101266 A CN 2010101101266A CN 201010110126 A CN201010110126 A CN 201010110126A CN 101954762 A CN101954762 A CN 101954762A
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Abstract
The invention discloses a steel strip plated with composite film containing cobalt nanowires and a preparation method thereof. the steel strip of the invention uses a steel strip as the substrate, and the both sides of the steel strip are respectively plated with a multilayer composite film containing cobalt nanowires. The bottom layer of each multilayer composite film containing cobalt nanowires is a micron crystalline nickle plating, the middle layer is a nickle composite plating containing cobalt nanowires and the surface layer is nanocrystalline nickle-cobalt alloy plating. The invention also provides the preparation method of the steel strip. The preparation method comprises the following steps: degreasing and activating a steel strip, adopting the direct current electroplating mode to prepare a micron crystalline nickle plating on the substrate, annealing, adopting the pulse electroplating mode to prepare a nickle composite plating containing cobalt nanowires on the nickle plating and then adopting the pulse injection mode to prepare a nanocrystalline nickle-cobalt alloy plating on the nickle composite plating containing cobalt nanowires. The steel strip is closely combined by the multilayer composite film containing cobalt nanowires and the low carbon steel strip, has good corrosion resistance, punching property and high load resistance and can be used as the shell material of the lithium ion power battery and high-performance alkaline Zn/MnO2 battery.
Description
Technical field
The present invention relates to a kind of plating steel band that contains the cobalt nanowire multi-layer compound film and preparation method thereof is arranged.
Background technology
Along with becoming increasingly conspicuous of problems such as environmental pollution, energy crisis and shortage of resources, development of technologies 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, it has caused people's extensive concern because of high-energy-density and high-rate discharge ability, not only on portable electric appts, be used widely, and be applied to electric automobile gradually, big-and-middle-sized electrical equipment aspect such as electric bicycle and electric tool.Especially wherein lithium-ion-power cell has become the main direction of each macrocell producer development at present.
The bump that electric automobile may run in the process of moving, jolt and at a high speed brake cause 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 electric automobile development.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 feasible method of security of lithium-ion-power cell problem.
The shell of lithium-ion-power cell is not only the container as a sealing, and it also has very important effect to the storge quality and the security performance of battery.Must have good electrolyte resistance corrosive nature as the battery container material.When running into bump, jolt and when at a high speed brake caused situation complicated and changeable such as strong concussion, box hat will bear thump load in short-term, so box hat plays bigger 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 to have ferro-nickel alloy plating on steel plate, and after punch forming, the coating of box hat sidewall and bottom has certain proportion requirement, satisfies the requirement of battery steel shell to decay resistance.
U.S. Pat 4760002 disclose a kind of on mild-carbon steel strip first plating one deck nickel film, then at plating one deck cobalt thin film, form the 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 problem of single solution battery container, and does not consider the anti-strong load demand as the power lithium-ion battery shell.
At Nano Letters 2007,7 (5): after most of metal material becomes the very large microcosmic nano wire of draw ratio from macro-size among D.X.Wang etc. " Where; and how; doesa nanowire break " that the people showed among the 1208-1212, the significant variation takes place in mechanical property, makes nano wire have better plasticity and ductility.
At Physical Review Letters1999,82:2900-2903.Hideyuki Ikeda, when waiting among " the Strain rateinduced amorpHization in metallic nanowires " that the people shows cobalt nanowire room temperature at 5%ps
-1Strain rate under the distortion after, its elasticity can reach 7.5%, yield stress can reach 5.5GPa, is higher than the block nickel material far away.When deformation took place, the 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 composited by one dimension nickel nano wire and two-dimentional nickel film and preparation method thereof.This nickel composite film has good mechanical performance and processing characteristics, can resist bigger shock loading, and have with low cost, advantage of simple technology.But directly plating one deck compound nickel film of containing nano wire has two big shortcomings on steel band, and the adhesion of the first and substrate is poor, and it two is that case hardness is not enough, scratches easily during punching press.
Summary of the invention
The object of the present invention is to provide a kind of plating that the steel band that contains the cobalt nanowire laminated film is arranged, this steel band has excellent corrosion resisting performance, punching performance and anti-strong load performance.
Another object of the present invention is to provide the preparation method of above-mentioned steel band.
The objective of the invention is to realize by following manner.
A kind of plating has the steel band that contains the cobalt nanowire multi-layer compound film, is substrate with the mild-carbon steel strip, at substrate both side surface plating the multi-layer compound film that contains cobalt nanowire is arranged.The bottom of multi-layer compound film is the brilliant nickel coating of micron, and crystallite dimension is 0.1～0.5 μ m, and thickness is 0.5～2 μ m; The intermediate layer is the nickel composite deposite that contains cobalt nanowire, and crystallite dimension is 50～100nm, and thickness is 0.5～1.5 μ m; The top layer is nanocrystalline nickel-cobalt alloy plating, and crystallite dimension is 20～50nm, and thickness is 0.1～0.5 μ m.
The content of cobalt nanowire is 0.5～5wt% in the described nickel composite deposite that contains cobalt nanowire, preferred wt 2%; Diameter is 20～40nm, and length is 0.5～1 μ m.Described cobalt nanowire 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%; Preferred 2wt%.
Above-mentioned plating has the preparation method of the steel band that contains the cobalt nanowire multi-layer compound film, may further comprise the steps:
(1) substrate surface preliminary treatment before the plating;
The substrate surface preliminary treatment is carried out chemical high temperature oil removing for earlier degreasing fluid being put in substrate before the plating; With the substrate surface flushing of distilled water after, put into activator again and activate then oil removing;
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, specimen surface is rinsed well, put into activator then and activate with distilled water;
Activator is: 1～5vol%HCl
Soak time: 0.5～2min.
(2) at the brilliant nickel coating of the two sides of substrate direct current electrode position micron:
The direct current electrode position plating bath is formed:
NiSO
4·7H
2O 250～300g/L；
NiCl
2·6H
2O 30～50g/L；
Boric acid 30～50g/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 afterwards at protective atmosphere (25%N
2+ 75%H
2) following annealing in process, 200～750 ℃ of annealing temperatures, annealing time 2～24h;
(4) steel band two sides pulse plating contains the nickel composite deposite of cobalt nanowire
A. contain the preparation of the nickel composite deposite plating bath of cobalt nanowire: take by weighing NiSO
47H
2O and NiCl
26H
2O is dissolved in the deionized water, and through magnetic agitation and heating, 60 ℃ of heating-up temperatures are dissolved mixture fully, obtain solution A; Take by weighing H
3BO
3Put into another container, add deionized water then, through magnetic agitation and heating, 60 ℃ of heating-up temperatures obtain transparent clear solutions B; Solution B is added solution A, add saccharin sodium again, magnetic agitation 20min, and then the adding diameter is 20～40nm, length is cobalt nanowire and the softex kw of 0.5～1 μ m, obtains containing the nickel composite deposite plating bath of suspension cobalt nanowire after ultrasonic wave stirs 30min.Described cobalt nanowire is prepared from by anodic oxidation aluminium formwork electro-deposition (AAO).
B. contain the preparation of the nickel composite deposite of cobalt nanowire: the plating bath that contains the suspension cobalt nanowire that step a is obtained is put into and is with hyperacoustic water bath with thermostatic control, 60 ℃ of thermostat temperatures, carry out ultrasonic agitation, then steel band is put into the composite deposite plating bath, connect the negative pole of power supply, positive pole connects the nickel plate, carries out composite plating, up to obtaining thickness is the nickel composite deposite that contains cobalt nanowire of 0.5～1.5 μ m, and outage finishes;
The nickel composite film plating bath that contains the suspension cobalt nanowire is formed:
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;
Cobalt nanowire 1～5g/L;
Softex kw 1.4～4.2 * 10
-3Mol (g cobalt nanowire)
-1The pulse plating technological parameter:
Average current density 3～5A/dm
2
i
on 5～50ms；
i
off 5～250ms；
Ultrasonic wave stirring frequency 40～60Hz;
Ultrasonic wave power of agitator 200～400W;
40～70 ℃ of temperature;
PH value 3.5～5.5;
(5) steel band two sides impulse jet nickel-cobalt alloy plating layer:
The impulse jet plating bath is formed:
NiSO
4·7H
2O 180～220g/L；
NiCl
2·6H
2O 40～60g/L；
CoSO
4·7H
2O 10～15g/L；
Boric acid 25～35g/L;
ALS 0.4～2g/L;
Butynediols 0.4～0.5ml/L;
Asccharin 0.8～1g/L;
The 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) washing, oven dry
The steel band that plating is good is clean with distilled water flushing, oven dry then.
(7) insulation dehydrogenation
The steel band that plating is good places and is incubated under 150～200 ℃ of conditions, to remove the hydrogen that produces in the coating in electroplating process.
More than the thickness of the time decision coating electroplated of each step.
The plating that is used for the power lithium-ion battery shell of the present invention has the steel band of the multi-layer compound film that contains cobalt nanowire, adopted multi-layer film structure, have higher intensity and case hardness, improved the bond strength of substrate and coating, reduced the coating porosity, improved the coating internal stress and distributed.
Because having carried out limiting effectively to the thickness of each layer film and the crystallite dimension that constitutes film, the inventor make material of the present invention obviously be different from the monolayer material of forming them or the peculiar character of traditional material often demonstrating aspect the decay resistance of mechanics, electricity, magnetics and material.On the one hand, when the crystal grain of forming film is little during to Nano grade, defectives such as crystal boundary and dislocation can increase, and the nucleating center of passivating film will be increased, thereby cause film surface that more passivating film is arranged; On the other hand, when the crystal grain of forming film is little during to Nano grade, the diffusion rate of ion can be higher, easier formation passivation layer, thus reduced the corrosion rate of film.More passivating film and lower corrosion rate finally make steel band have excellent corrosion resisting performance.Compound cobalt nanowire in the nano-crystal nickel film can form more crystal boundary.Therefore, have the multilayer film that contains the Ni-based laminated film of cobalt nanowire, can obviously improve the decay resistance of battery container.
Generally, along with the reducing nano wire and can embody of size, mainly show as elasticity and plasticity and all improve greatly than the better mechanical property of massive material.Compound cobalt nanowire in the nano-crystal nickel film can be implemented under the situation that does not reduce coating surface hardness the overall flexibility, punching performance, surface scratch resistance energy and the anti-strong load performance that improve coating and the raising used for electric vehicle power lithium-ion battery security performance when strong load such as being clashed into.
The plating that makes with the inventive method has the steel band that contains the cobalt nanowire laminated film not only to have good percentage elongation and corrosion resistance, and coating surface hardness height, overall flexibility good, be beneficial to punch forming, therefore can be used as the case material of lithium-ion-power cell and other heavy-duty batteries.
The brilliant nickel coating of micron of bottom of the present invention is prepared from by the technology of direct current electrode position, can combine well with substrate after annealing in process, can effectively prevent coming off of coating.Its crystallite dimension is 0.1～0.5 μ m, elite 0.5～2 μ m of thickness.Nickel coating can not play the corrosion-resistant effect well under the situation of thickness less than 0.5 μ m; 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 that contains cobalt nanowire in intermediate layer is that (1～5g/L) cobalt nanowire joins in the plating bath that configures, and is prepared from by pulse plating again with finite concentration.Because cobalt nanowire has good toughness, the nickel composite deposite that contains cobalt nanowire can improve the toughness of coating when not reducing the multilayer film surface hardness, improve the anti-strong load-carrying ability of battery container then.The thickness that contains the nickel composite deposite of cobalt nanowire is 0.5～1.5 μ m.
The nanocrystalline nickel-cobalt alloy plating on top layer is electroplated by impulse jet and is prepared from, 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, electrical conductivity is than characteristics such as height.The nanocrystalline nickel-cobalt alloy plating that possesses these characteristics is applied in the inner surface of battery container, can obviously improves the Corrosion Protection and the electric property of battery container; Be applied to the outer surface of battery container, can reduce the surface tear in the punching course, reduce coefficient of friction, more help the streamline production of battery container, enhance productivity.
The beneficial effect of the invention:
The nickel composite deposite that contains cobalt nanowire can improve the toughness of multilayer film coating and the anti-strong load-carrying ability of battery container when not reducing the multilayer film surface hardness.Generally, along with reducing of size, nano wire can embody than the better mechanical property of massive material.Compound cobalt nanowire in nickel coating can improve the toughness of coating, thereby has improved the punching performance and the surface scratch resistance energy of steel band.Strike out battery case with this kind steel band, after the assembling battery, can improve the security performance of used for electric vehicle lithium-ion-power cell when strong load such as being clashed into.
Description of drawings
Fig. 1 is the structural representation of steel band of the present invention, and wherein 1 is substrate; 2 is bottom; 3 is the intermediate layer; 4 is the top layer;
Fig. 2 is a process chart of the present invention.
The specific embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Steel band of the present invention is substrate 1 with the mild-carbon steel strip, and plating has the multi-layer compound film that contains cobalt nanowire on the steel band two sides; The bottom 2 of described multi-layer compound film is that crystallite dimension is 0.1～0.5 μ m, and thickness is the brilliant nickel coating of micron of 0.5～2 μ m; Intermediate layer 3 is that crystallite dimension is 50～100nm, and thickness is the nickel composite deposite that contains cobalt nanowire of 0.5～1.5 μ m; Top layer 4 is that crystallite dimension is 20～50nm, and thickness is the nanocrystalline nickel-cobalt alloy plating of 0.1～0.5 μ m.See Fig. 1.
The concrete preparation process of above-mentioned steel band is specific as follows: (see figure 2)
The thickness of selecting for use Shanghai Baoshan Iron ﹠ Steel Co., Ltd to produce is that the BDCK battery special steel strip of 0.25mm is as electroplated substrates.Its chemical composition is: C:0.029% (% represents percetage by weight, down together)
Si：0.02％
Mn：0.2％
P：0.09％
S：0.003％
Al：0.06％。
1, plating front surface preliminary treatment
In order to make coating and substrate form good binding, 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 processing.This example adopts chemical high temperature deoiling method.
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 ℃
The oil removing time: 3min
After the oil removing fully, specimen surface is rinsed well, put into activator again and activate with distilled water.
Activator is formed: 3vol%HCl
Soak time: 1min.
2, the brilliant nickel coating of direct current electrode position micron
The direct current electrode position plating bath is formed:
NiSO
4·7H
2O 280g/L；
NiCl
2·6H
2O 40g/L；
Boric acid 40g/L;
The direct current electrode position technological parameter:
Current density: 4A/dm
2
PH value: 4
Anode: nickel plate
Temperature: 50 ℃
Time: 60s
Under these conditions, it is 0.1～0.5 μ m that crystallite dimension is prepared in the steel band both sides, and thickness is the brilliant nickel coating of micron of 0.8 μ m.
3, annealing in process
With electroplate steel band after the brilliant nickel coating of micron place box-annealing furnace protective atmosphere (25%N
2+ 75%H
2) following annealing in process.400 ℃ of annealing temperatures, annealing time 12h.
4, steel band two sides pulse plating is mixed with the nickel composite deposite of cobalt nanowire
A. contain the preparation of the nickel composite deposite plating bath of cobalt nanowire: take by weighing NiSO
47H
2O and NiCl
26H
2O is dissolved in the deionized water, and through magnetic agitation and heating, 60 ℃ of heating-up temperatures are dissolved mixture fully, obtain solution A; Take by weighing H
3BO
3Put into another container, add deionized water then, through magnetic agitation and heating, 60 ℃ of heating-up temperatures obtain transparent clear solutions B; Solution B is added solution A, add saccharin sodium again, magnetic agitation 20min, and then the adding diameter is 20～40nm, length is cobalt nanowire and the softex kw of 0.5～1 μ m, obtains containing the nickel composite deposite plating bath of suspension cobalt nanowire after ultrasonic wave stirs 30min;
B. contain the preparation of the nickel composite deposite of cobalt nanowire: the plating bath that contains the suspension cobalt nanowire that step a is obtained is put into and is with hyperacoustic water bath with thermostatic control, 60 ℃ of thermostat temperatures, carry out ultrasonic agitation, then steel band is put into the composite deposite plating bath, the negative pole that connects power supply, positive pole connects the nickel plate, carries out composite plating.
The nickel composite film plating bath that contains the suspension cobalt nanowire is formed:
NiSO
4·7H
2O 250g/L
NiCl
2·6H
2O 50g/L
H
3BO
3 35g/L
Saccharin sodium 1.2g/L
Cobalt nanowire 3g/L
Softex kw 4.2 * 10
-3Mol
The pulse plating technological parameter:
Average current density 4A/dm
2
i
on 30ms
i
off 120ms
Ultrasonic wave stirring frequency 50Hz
Ultrasonic wave power of agitator 300W
60 ℃ of temperature
Anode nickel plates
Time: 60s
Under these conditions, it is 50～100nm that one deck crystallite dimension is prepared in the steel band both sides, and thickness is the nickel composite film coating of the suspension cobalt nanowire of 0.8 μ m.
5, impulse jet nickel-cobalt alloy plating coating
Plating bath is formed: NiSO
47H
2O 200g/L
NiCl
2·6H
2O 50g/L
CoSO
4·7H
2O 12g/L
Boric acid 30g/L
ALS 1.2g/L
Butynediols 0.5ml/L
Asccharin 0.8g/L
The 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
Under these conditions, it is 20～50nm that one deck crystallite dimension is prepared in the steel band both sides, and thickness is the plating nickel-cobalt alloy coating of 0.5 μ m.
6, washing, oven dry
The steel band that plating is good is clean with distilled water flushing, oven dry then.
7, insulation dehydrogenation
The steel band that plating is good places and is incubated under 200 ℃ of conditions, to remove the hydrogen that produces in the coating in electroplating process.
Experimental data is as shown in the table.Following table 1 is the neutral salt spray test contrast of present embodiment gained steel band and BDCK steel band.
Table 1 neutral salt spray test tables of data
| 4 hours | 8 hours | 12 hours | 16 hours | 20 hours | 24 hours |
| Embodiment | No |
1 |
3 |
4 rust spots | 8 rust spots | 11 rust spots, rust spot become |
| BDCK | ||||||
| 1 |
2 rust spots | 5 rust spots | 13 rust spots | 31 rust spots, rust spot become big | Heavy corrosion |
Claims (8)
1. a plating has the steel band that contains the cobalt nanowire multi-layer compound film, it is characterized in that, and with the mild-carbon steel strip substrate (1), plating has the multi-layer compound film that contains cobalt nanowire on the steel band two sides; The bottom of described multi-layer compound film (2) is that crystallite dimension is 0.1～0.5 μ m, and thickness is the brilliant nickel coating of micron of 0.5～2 μ m; Intermediate layer (3) is that crystallite dimension is 50～100nm, and thickness is the nickel composite deposite that contains cobalt nanowire of 0.5～1.5 μ m; Top layer (4) is that crystallite dimension is 20～50nm, and thickness is the nanocrystalline nickel-cobalt alloy plating of 0.1～0.5 μ m.
2. plating according to claim 1 has the steel band that contains the cobalt nanowire multi-layer compound film, it is characterized in that, the diameter of cobalt nanowire is 20～40nm in the described nickel composite deposite that contains cobalt nanowire, and length is 0.5～1 μ m.
3. plating according to claim 1 has the steel band that contains the cobalt nanowire multi-layer compound film, it is characterized in that, the content of cobalt nanowire is 0.5～5wt% in the described nickel composite deposite that contains cobalt nanowire.
4. according to claim 1 or 2 or 3 described plating the steel band that contains the cobalt nanowire multi-layer compound film is arranged, it is characterized in that, the content of cobalt nanowire is 2wt% in the described nickel composite deposite that contains cobalt nanowire.
5. plating according to claim 1 has the steel band that contains the cobalt nanowire multi-layer compound film, it is characterized in that, the cobalt content of described nanocrystalline nickel-cobalt alloy plating is 0.5～5wt%.
6. plating has the steel band that contains the cobalt nanowire multi-layer compound film according to claim 1 or 5, it is characterized in that, the cobalt content of described nanocrystalline nickel-cobalt alloy plating is 2wt%.
7. the described a kind of plating of claim 1 has the preparation method of the steel band that contains the cobalt nanowire multi-layer compound 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 direct current electrode position plating bath is formed:
NiSO
4·7H
2O 250～300g/L；
NiCl
2·6H
2O 30～50g/L；
Boric acid 30～50g/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 afterwards at 25%N
2+ 75%H
2Annealing in process under the protective atmosphere, 200 ℃～750 ℃ of annealing temperatures, annealing time 2～24h;
[4] the steel band two sides pulse plating after annealing in process is mixed with the nickel composite deposite of cobalt nanowire;
[5] two sides impulse jet nickel-cobalt alloy plating layer
The impulse jet plating bath is formed:
NiSO
4·7H
2O 180～220g/L；
NiCl
2·6H
2O 40～60g/L；
CoSO
4·7H
2O 10～15g/L；
Boric acid 25～35g/L;
ALS 0.4～2g/L;
Butynediols 0.4～0.5ml/L;
Asccharin 0.8～1g/L;
The 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] washing, oven dry
The steel band that plating is good is clean with distilled water flushing, oven dry then;
[7] insulation dehydrogenation
The steel band of oven dry is placed under 150～200 ℃ of conditions and is incubated, to remove the hydrogen that in electroplating process, produces in the coating.
8. plating according to claim 7 has the preparation method of the steel band that contains the cobalt nanowire multi-layer compound film, it is characterized in that, described step [4] specifically may further comprise the steps:
A. contain the preparation of the nickel composite deposite plating bath of cobalt nanowire: take by weighing NiSO
47H
2O and NiCl
26H
2O is dissolved in the deionized water, and through magnetic agitation and heating, 60 ℃ of heating-up temperatures are dissolved mixture fully, obtain solution A; Take by weighing H
3BO
3Put into another container, add deionized water then, through magnetic agitation and heating, 60 ℃ of heating-up temperatures obtain transparent clear solutions B; Solution B is added solution A, add saccharin sodium again, magnetic agitation 20min, and then the adding diameter is 20～40nm, length is cobalt nanowire and the softex kw of 0.5～1 μ m, obtains containing the nickel composite deposite plating bath of suspension cobalt nanowire after ultrasonic wave stirs 30min;
B. contain the preparation of the nickel composite deposite of cobalt nanowire: the plating bath that contains the suspension cobalt nanowire that step a is obtained is put into and is with hyperacoustic water bath with thermostatic control, 60 ℃ of thermostat temperatures, carry out ultrasonic agitation, then steel band is put into the composite deposite plating bath, connect the negative pole of power supply, positive pole connects the nickel plate, carries out composite plating, up to obtaining thickness is the nickel composite deposite that contains cobalt nanowire of 0.5～1.5 μ m, and outage finishes;
The nickel composite film plating bath that contains the suspension cobalt nanowire is formed:
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;
Cobalt nanowire 1～5g/L;
Softex kw 1.4～4.2 * 10
-3Mol (g cobalt nanowire)
-1
The pulse plating technological parameter:
Average current density 3～5A/dm
2
i
on 5～50ms；
i
off 5～250ms；
Ultrasonic wave stirring frequency 40～60Hz;
Ultrasonic wave power of agitator 200～400W;
40～70 ℃ of temperature;
PH value 3.5～5.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN103233251A (en) * | 2013-04-24 | 2013-08-07 | 秦皇岛首钢长白结晶器有限责任公司 | Method for electroforming Co-Ni alloy coating on copper plate for continuous casting crystallizer |
| CN108048882A (en) * | 2017-12-07 | 2018-05-18 | 天津大学 | A kind of method that graphical cobalt nanowire array is prepared based on anodic oxidation aluminium formwork method |
| CN110029373A (en) * | 2019-05-24 | 2019-07-19 | 山东金宝电子股份有限公司 | A kind of compound additive for eliminating the unusual coarsening crystallization of electrolytic copper foil |
| WO2020009212A1 (en) * | 2018-07-06 | 2020-01-09 | 日本製鉄株式会社 | Surface-treated steel sheet and method for producing surface-treated steel sheet |
| WO2020009213A1 (en) * | 2018-07-06 | 2020-01-09 | 日本製鉄株式会社 | Surface-treated steel sheet and method for manufacturing surface-treated steel sheet |
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| WO2020009212A1 (en) * | 2018-07-06 | 2020-01-09 | 日本製鉄株式会社 | Surface-treated steel sheet and method for producing surface-treated steel sheet |
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| JPWO2020009213A1 (en) * | 2018-07-06 | 2020-07-09 | 日本製鉄株式会社 | Surface-treated steel sheet and method for producing surface-treated steel sheet |
| JPWO2020009212A1 (en) * | 2018-07-06 | 2020-07-09 | 日本製鉄株式会社 | Surface-treated steel sheet and method for producing surface-treated steel sheet |
| CN110029373A (en) * | 2019-05-24 | 2019-07-19 | 山东金宝电子股份有限公司 | A kind of compound additive for eliminating the unusual coarsening crystallization of electrolytic copper foil |
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