CN101954763A - 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 PDF

Info

Publication number
CN101954763A
CN101954763A CN201010110136XA CN201010110136A CN101954763A CN 101954763 A CN101954763 A CN 101954763A CN 201010110136X A CN201010110136X A CN 201010110136XA CN 201010110136 A CN201010110136 A CN 201010110136A CN 101954763 A CN101954763 A CN 101954763A
Authority
CN
China
Prior art keywords
nickel
nickeliferous
nano wire
plating
steel band
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201010110136XA
Other languages
Chinese (zh)
Other versions
CN101954763B (en
Inventor
周益春
潘勇
王建兴
李玮
周兆峰
堵艳艳
杜超
王子涵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Yongsheng New Materials Co ltd
Original Assignee
Xiangtan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiangtan University filed Critical Xiangtan University
Priority to CN201010110136XA priority Critical patent/CN101954763B/en
Publication of CN101954763A publication Critical patent/CN101954763A/en
Application granted granted Critical
Publication of CN101954763B publication Critical patent/CN101954763B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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

A kind of plating has steel band of nickeliferous nano wire laminated film and preparation method thereof
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 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, lithium ion battery has caused people's extensive concern because of its high-energy-density and high-rate discharge ability, not only on portable electric appts, be used widely, and being applied to big-and-middle-sized electrical equipment aspects such as electric automobile, electric bicycle and electric tool gradually, 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 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 security of lithium-ion-power cell problem.
Shell as lithium-ion-power cell not only will have good electrolyte resistance corrosive nature, and the 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 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 ferro-nickel alloy plating on steel plate, and after the 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, and then plating one deck cobalt thin film forms 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 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 among D.X.Wang etc. " Where; and how; does a nanowire break " that the people showed among the 1208-1212, 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 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 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 excellent corrosion resisting performance, 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, with the mild-carbon steel strip is substrate (1), and described mild-carbon steel strip is the BDCK battery special steel strip that Shanghai Baoshan Iron ﹠ Steel 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 a 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 binding 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 that 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, specimen surface is rinsed well, put into 1～5vol%HCl activation, 0.5～2min then, for electroplating reaction provides active surface with distilled water.The taking-up sample is electroplated after cleaning with distilled water once more immediately.
2, dc source is electroplated the brilliant nickel dam bottom of micron:
Plating bath is formed:
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) following 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.Concrete technological parameter is as follows:
The nickel composite film plating bath that contains suspension nickel nano wire 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
Nickel nano wire 1～5g/L
Softex kw 1.4～4.2 * 10 -3Mol (g nickel nano wire) -1
The pulse plating technological 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 technological parameter is as follows:
Plating bath is formed: 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, oven dry then.
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 again in the outside that contains the nano wire laminated film, 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 limiting effectively to the thickness of the film of each layer and the crystallite dimension of formation film, makes material of the present invention demonstrate 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 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 increase, 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 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 excellent corrosion resisting performance.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, shows that mainly elasticity and plasticity all improve greatly.Compound nickel nano wire in the nickel coating of MULTILAYER COMPOSITE coating, can be implemented under 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 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 surface of good 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 Iron ﹠ Steel 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 binding by the technology 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 under 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 the good mechanical performance, 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.Characteristics such as nanocrystalline nickel-cobalt alloy plating has surfacing, densification, porosity is low, crystal grain is tiny, hardness is high, electrical conductivity height.Because the nanocrystalline nickel-cobalt alloy plating in top layer has the passivating film nucleating point of higher density, thereby make nanocrystalline coating have high-quality passivating film and lower corrosion rate, be applied in the inner surface of battery container, can obviously improve the decay resistance 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 owing to its surfacing, hardness height.
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 a 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 for use Shanghai Baoshan Iron ﹠ Steel 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, down together)
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 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 formed:
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 then and activate with distilled water.
Activator is formed: 3vol%HCl
Soak time: 1min
(the brilliant nickel coating of direct current electrode position micron)
Plating bath is formed:
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) following 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 (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 certain amount of H 3BO 3Put into another container, add small amount of deionized water then,, obtain transparent clear solutions B through magnetic agitation and appropriate heating; Solution B is added solution A, add a certain amount of saccharin sodium again, 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, there is plating the steel band of the brilliant nickel of micron to put into the laminated film plating bath then, 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 is formed:
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 technological parameter:
Average current density 4A/dm 2
i on 30ms
i off 120ms
60 ℃ of temperature
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 is formed: 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, oven dry then.
(insulation dehydrogenation)
The steel band that plating is good places 200 ℃ of insulations down, 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 sample in the following manner, as a comparative example.
Comparative example preparation method: select substrate identical and plating pre-treating method for use with embodiment.Adopt the method for direct current electrode position, equal plating one 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 and handle, 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 No rust spot 1 rust spot 2 rust spots 4 rust spots 8 rust spots 12 rust spots, rust spot become big
BDCK
1 rust spot 2 rust spots 5 rust spots 13 rust spots 31 rust spots, rust spot become big Heavy corrosion

Claims (6)

1. a plating has the steel band of nickeliferous nano wire laminated film, it is characterized in that, and with the mild-carbon steel strip substrate, the multilayer film of nickeliferous nano wire is 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 that 0.5～1.5 μ m top layer is nanocrystalline nickel-cobalt alloy plating, and crystallite dimension is that 20～50nm, thickness are 0.1～0.5 μ m.
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 anodic oxidation aluminium formwork electro-deposition (AAO).
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. the described plating of 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 is formed:
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 afterwards at protective atmosphere (25%N 2+ 75%H 2) following annealing in process, 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;
5) at the two sides of steel band impulse jet nickel-cobalt alloy plating coating:
The plating bath of impulse jet is formed: 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 oven dry places under 150～200 ℃ of conditions again and is incubated dehydrogenation then.
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 earlier degreasing fluid being put in substrate before the described plating of step 1); Rinse well with the substrate surface of distilled water after then, put into activator and activate 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.
6. plating according to claim 4 has the preparation method of the steel band of nickeliferous nano wire laminated film, it is characterized in that, step 4) 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, and makes solids dissolve fully, obtains solution A; With H 3BO 3Put into another container, add deionized water then, stir, obtain transparent clear solutions B; Solution B is added solution A, add saccharin sodium again, stir 20min, and then the diameter that adding is prepared from by the alumina formwork method is 20～40nm, 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:
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 Ni nano wire) -1
(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, there is plating the steel band of the brilliant nickel of micron to put into the laminated film plating bath of step (1) then, the negative pole that connects power supply, positive pole connects the nickel plate, carries out composite plating;
The pulse plating technological 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;
Anode nickel plates
Ultrasonic wave stirring frequency 40～60Hz;
Ultrasonic wave power of agitator 200～400W.
CN201010110136XA 2010-02-10 2010-02-10 Nickeliferous nanowire laminated film plated steel belt and production method thereof Active CN101954763B (en)

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 true CN101954763A (en) 2011-01-26
CN101954763B CN101954763B (en) 2013-03-13

Family

ID=43482474

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201010110136XA Active CN101954763B (en) 2010-02-10 2010-02-10 Nickeliferous nanowire laminated film plated steel belt and production method thereof

Country Status (1)

Country Link
CN (1) CN101954763B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN104164685A (en) * 2014-06-11 2014-11-26 安徽长青电子机械（集团）有限公司 Method for plating nickel on steel plate
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
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
CN109477234A (en) * 2016-07-18 2019-03-15 巴斯夫欧洲公司 Cobalt plating composition comprising the additive filled for tight submicrometer structure
CN115787014A (en) * 2022-11-30 2023-03-14 江苏东方九天新能源材料有限公司 Surface treatment process for battery nickel-plated steel strip

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN201619267U (en) * 2010-02-10 2010-11-03 湘潭大学 Steel strip coated with composite films containing nickel nanowires

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN201619267U (en) * 2010-02-10 2010-11-03 湘潭大学 Steel strip coated with composite films containing nickel nanowires

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN104164685A (en) * 2014-06-11 2014-11-26 安徽长青电子机械（集团）有限公司 Method for plating nickel on steel plate
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
CN109477234B (en) * 2016-07-18 2021-12-10 巴斯夫欧洲公司 Cobalt plating compositions comprising additives for void-free sub-micron structure filling
CN109477234A (en) * 2016-07-18 2019-03-15 巴斯夫欧洲公司 Cobalt plating composition comprising the additive filled for tight submicrometer structure
TWI737772B (en) * 2016-07-18 2021-09-01 德商巴斯夫歐洲公司 Composition for cobalt plating comprising additive for void-free submicron feature filling
TWI782639B (en) * 2016-07-18 2022-11-01 德商巴斯夫歐洲公司 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
CN115787014A (en) * 2022-11-30 2023-03-14 江苏东方九天新能源材料有限公司 Surface treatment process for battery nickel-plated steel strip
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

Also Published As

Publication number Publication date
CN101954763B (en) 2013-03-13

Similar Documents

Publication Publication Date Title
CN101954763B (en) Nickeliferous nanowire laminated film plated steel belt and production method thereof
CN102148339B (en) Nickel-cobalt/nickel/nickel-cobalt multilayer film plated battery shell steel strip and preparation method thereof
TW445663B (en) A method of surface treatment for a battery container, a surface treated steel sheet for a battery container, a battery container and a battery using thereof
CN101205623B (en) Nano compound electroplating new method for preservation of neodymium iron boron ferrite
CN102260891B (en) Method for electrodepositing nanocrystalline nickel-cobalt alloy by double-pulse
CN102009504B (en) Steel strip plated with multi-layer micron/nano-crystal nickel films and preparation method thereof
CN101954762B (en) Steel strip plated with composite film containing cobalt nanowires and preparation method thereof
CN102773434A (en) Nanocomposite electroplating layer copper plate of continuous casting crystallizer and preparation process of nanocomposite electroplating layer copper plate
CN104233420A (en) Method for directly electroplating high-binding-force nickel layer on surface of aluminum or aluminum alloy
CN105063685B (en) A kind of nickel plating copper material of nickel and cobalt containing alloy layer and its preparation method and application
CN102230200A (en) Cobalt-containing nickel plated steel strip serving as lithium battery shell material and preparation method thereof
CN101826675B (en) Material for shell of connector and preparation method thereof
CN102094223B (en) Si3N4 nanoparticle-containing nanostructured Ni-based composite film material and preparation method thereof
JP7085394B2 (en) Laminated electrolytic foil
CN202088562U (en) Tin-soldering aluminum tape with high-corrosion resistance
CN105449180B (en) A kind of aluminium/copper/tin/graphite sandwich construction lithium ion battery negative material and preparation method thereof
CN1676674A (en) Method for preparing nickel-phosphor alloy base composite cladding containing nano particle
CN201619267U (en) Steel strip coated with composite films containing nickel nanowires
CN101958404B (en) Nanowire-containing multilayer composite thin film plated steel belt and preparation method thereof
CN106848198B (en) A kind of preparation method of lithium battery cathode pole piece
CN201616461U (en) Cobalt-containing nanowire composite film plated steel band
CN201626156U (en) Steel strip plated with multiple layers of composite films containing nanowires
CN101967668A (en) Method for preparing Ni-P-UFD composite coating by chemical plating or electroplating process
CN201616462U (en) Steel belt used as battery casing and plated with multilayer laminated film containing cobalt nanowires
CN201856419U (en) Battery shell steel belt plated with nickel-cobalt/nickel/nickel-cobalt multilayer films

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20230902

Address after: 412007 No. 599 Wanxian Road, Tianyuan District, Zhuzhou City, Hunan Province

Patentee after: HUNAN YONGSHENG NEW MATERIALS Co.,Ltd.

Address before: 411105 in Hunan Province in the western suburbs of Xiangtan City Gu Tong sheep

Patentee before: XIANGTAN University