CN101958404B - Nanowire-containing multilayer composite thin film plated steel belt and preparation method thereof - Google Patents
Nanowire-containing multilayer composite thin film plated steel belt and preparation method thereof Download PDFInfo
- Publication number
- CN101958404B CN101958404B CN201010110129XA CN201010110129A CN101958404B CN 101958404 B CN101958404 B CN 101958404B CN 201010110129X A CN201010110129X A CN 201010110129XA CN 201010110129 A CN201010110129 A CN 201010110129A CN 101958404 B CN101958404 B CN 101958404B
- Authority
- CN
- China
- Prior art keywords
- plating
- nickel
- layer
- coating
- nano wire
- 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.)
- Active
Links
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
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a nanowire-containing multilayer composite thin film plated steel belt and a preparation method thereof. The steel belt is specifically applied to a battery outer shell material of a mercury-free alkaline battery, a lithium ion battery, a nickel-metal hydride battery and the like and also applied to the field of chemical industry, electrons, packaging, magnetic materials and the like. The preparation method comprises the following steps of: on one face of a steel belt serving as a substrate, plating a layer of micron-crystalline nickel as an outer bottom layer in a DC plating way, wherein the face corresponds tothe outer surface of a battery shell, plating a layer of micron-crystalline nickel serving as an outer middle layer in a pulse plating way, and plating a layer of nano-crystalline nickel-cobalt alloy layer serving as an outer surface layer in a pulse injection plating way; and on one face of the steel belt corresponding to the inner surface of the battery shell, plating a layer of micron-crystalline nickel coated layer as an inner bottom layer in the DC plating way; plating a layer of nanowire-containing nickle composite thin film as an inner middle layer in the pulse plating way, and plating a layer of nano-crystalline nickel-cobalt alloy layer as an inner surface layer in the pulse injection plating way. The steel belt prepared by the invention has the advantages of good corrosion resistance and pressing resistance.
Description
Technical field
The present invention relates to a kind of plating that is used for battery container steel band of the multi-layer compound film that contains nano wire and preparation method thereof is arranged.
Background technology
In recent years, Along with people's requires increasingly highly to battery performance, and the performance of the case material of batteries such as alkaline Mn cell, Ni-MH battery and lithium-ion-power cell also more and more receives numerous professional persons' concern.The alkaline Mn cell shell is as the container of a sealing, because the filling of strong basicity electrolyte requires it that enough strong decay resistance is arranged.In addition, battery case also serves as battery plus plate current-collecting body in alkaline Mn cell, so the internal resistance of battery case also is a key factor that influences battery performance.In addition, battery case also will be participated in the reaction of alkaline electrolyte.
Disclose a kind of process for treating surface of battery case steel plate among the patent ZL97198580.4, electroplated one deck nickel at steel plate corresponding to a side that forms the battery container inwall, and then electroplated one deck tin layer, annealing at last forms the nickel-tin alloy layer at the battery inwall.The nickel-tin alloy layer is applied to the inwall of battery container, can effectively reduce the internal resistance of battery container, but after itself and the alkaline matter Long contact time, discharge performance can variation.
Patent CN1600904A discloses a kind of nickel-plated deeply-draw steel strip and production method thereof; Continuous electroplating 2～3 μ m nickel coatings on mild-carbon steel strip; Handle through heat treatment and laser-impact; Make nickel coating and base material form nickel/iron diffusion layer, obtain the corrosion-resistant steel band of required size then through finishing procedure through thermal diffusion.The coating elongation is not less than 8%, and decay resistance reaches 8 grades, has good elongation and decay resistance, is mainly used in the heavy-duty battery sheathing material.But single nickel coating is easy to occur powder phenomenon-tion in the punch forming process of battery case, can increase the defective of battery case sidewall, shortens the life-span of mould and drift.
A kind of surface of steel plate treatment technology at the inside and outside wall plating of battery container nickel-cobalt alloy is disclosed among the patent ZL97194368.0.Because traditional single nickel coating powder phenomenon-tion in the punch forming process of battery container is serious; Cause battery container sidewall defective to increase; Drift and die life shorten, and production efficiency reduces, and replace single nickel coating then can reduce powder phenomenon-tion significantly with nickel-cobalt alloy.But the hardness of nickel-cobalt alloy coating is very big; Be generally HV310 ± 10, and the hardness of mild steel substrate commonly used is HV120 ± 10, coating and substrate hardness differ too big; The hardness number mismatch is serious, causes in the punch forming process of battery container, occurring the coating obscission easily.
A kind of process for treating surface of battery case steel plate is disclosed among the patent ZL99809927.9; Electroplate one deck nickel at steel plate corresponding to a side that forms the battery case inwall; And then electroplate one deck bismuth layer, last annealing in process forms nickel-bismuth alloy layer in the battery inner walls.After bismuth metal and the alkaline solution Long contact time, electrodeposited coating can not dissolve, but bismuth coating comes off easily, and the phenomenon that nickel-bismuth alloy can not occur coming off.Nickel-bismuth alloy layer is applied to the inwall of battery container, can obviously improve the decay resistance of battery container in alkaline environment.But the electric conductivity of bismuth is very poor, the application of nickel-bismuth alloy, the internal resistance that has increased the battery container inwall.
Zhang Xian; People such as Xu Yijun mention in " performance of the alkaline Mn cell of box hat electroplated Ni (Bi) and annealing in process " literary composition; Nickel coating has stronger adhesion property and decay resistance on the box hat surface; But relatively poor with the contact performance of anode ring, nickel-phosphorus, nickel-tin alloy can improve contact performance, but decay resistance is relatively poor.Bismuth is stable in alkaline solution, and is good with the contact performance of positive electrode active materials EMD, and heating condition diffusion easily down, is easy to form alloy.Also mention in the literary composition, annealing can increase the internal resistance of nickel coating, and because the formation of nickel-ferro alloy, nickel coating thickness descends, and causes the contact performance of box hat and anode ring and decay resistance to descend.
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.
Because steel band top layer coating requires to have higher hardness, thus the high metal or alloy coating of hardness generally adopted, and adopt a series of technology to make prepared top layer coating have less crystallite dimension, coating is fine and close.Yet such coating often has higher internal stress, can reduce the toughness of coating like this, causes brittle coating.
Well behaved alkaline battery has the harsh requirement of comparison to its case material.Because the strong basicity electrolyte of alkaline battery is filled, therefore require case material that good alkali corrosion resistance performance is arranged.Battery container requires it to have lower internal resistance as plus plate current-collecting body, and can the excellent contact performance be arranged with positive electrode material, and this has conductivity preferably with regard to the case material that requires to make battery, and surface hardness is high.Why want case material to have higher surface hardness; Be because the high material of surface hardness forms trickle crackle at the battery container inwall easily in battery punch forming process; Be equivalent to increase the contact area of battery container and positive electrode material, improved the contact performance of battery container and positive electrode material, simultaneously; The crackle that is produced has good lubricant retentivity, makes the housing demoulding more easy.Battery container is very big in the deformation drag of punching course, if when the adhesion of coating and substrate is bad, is easy to occur the phenomenon that coating comes off.In addition, if when the powder performance of coating is relatively poor, promptly coating forms more powder in the ironing process, and these powder adherence can cause defective to the battery case sidewall on drift.
The process for treating surface of conventional battery housing steel band all is single nickel coating or duplicature design simple in structure.These technological shortcomings are that when possessing some advantage, also there are some shortcomings bigger to the battery container performance impact in after treatment steel band.For example, traditional nickel plated steel strip, its corrosion resistance and good combines well with substrate, but its powder performance is relatively poor, promptly in punching course, forms powder easily.The steel band of plated nickel and nickel-cobalt alloy because the hardness of nickel-cobalt alloy is big, causes the hardness number of coating and substrate not match; In punching course, occurring coating easily comes off; The coating that hardness is high in addition often has higher internal stress, can reduce the toughness of coating like this, causes brittle coating.The steel band of plated nickel and nickel-bismuth alloy, its alkali corrosion resistance performance is good, but because the poorly conductive of bismuth causes the internal resistance of battery container big.The steel band of plated nickel and nickel-tin alloy, its internal resistance is little, but because the alkali corrosion resistance poor performance of nickel-tin alloy, after battery container and alkaline electrolyte Long contact time, the guiding discharge degradation.
Summary of the invention
The object of the present invention is to provide a kind of steel band with excellent corrosion resisting performance, punching performance of combining closely and forming by MULTILAYER COMPOSITE coating that contains nano wire and mild-carbon steel strip that is used for battery container.
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 through following manner.
The present invention has the steel band of the multi-layer compound film that contains nano wire as the plating of battery case; With the steel band is substrate; Steel band corresponding to the one side of battery container outer surface on the brilliant nickel coating of plating one deck micron as outside bottom, the coating crystallite dimension is 0.1～0.5 μ m, thickness is 0.5～2.0 μ m; Plating one deck nano-crystal nickel coating is as outer middle layer, and the crystallite dimension of coating is 50～100nm, and thickness is 1～2 μ m; The nanocrystalline nickel-cobalt alloy layer of plating one deck is as extexine, and crystallite dimension is 20～50nm, and thickness is 0.1～1 μ m.At steel band corresponding to the brilliant nickel coating of side surface one deck micron of battery container inner surface as interior bottom, the coating crystallite dimension is 0.1～0.5 μ m, thickness is 0.5～2.0 μ m; Plating one deck contains the nickel composite film of nano wire as interior intermediate layer, and the crystallite dimension of coating is 50～100nm, and thickness is 0.5～1.5 μ m; The nanocrystalline nickel-cobalt alloy coating of plating one deck is as the endosexine, and the coating crystallite dimension is 20～50nm, and thickness is 0.1～1 μ m.Described nano wire is one or more in nickel nano wire, cobalt nanowire, the bismuth nano-wire.Be preferably bismuth nano-wire, because bismuth has better alkali corrosion resistance performance.
Nano wire is prepared from through anodic oxidation aluminium formwork electro-deposition (AAO) in the described nickel composite deposite that contains nano wire.Content is 0.5～5wt%, is preferably 2wt%.The diameter of nano wire is 20～40nm, and length is 0.5～1 μ m.
The cobalt content of the nickel-cobalt alloy coating of described endosexine and extexine is 0.5～5wt%.Be preferably 2wt%.
The preparation method of above-mentioned steel band is following:
One, mild-carbon steel strip is plated pre-treatment
Adopt chemical high temperature deoiling method, after the oil removing fully, specimen surface is rinsed well, put into activator then and carry out activation with distilled water.The taking-up sample is electroplated after cleaning with distilled water once more at last immediately.
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 carry out activation with distilled water;
Activator is: 1～5vol%HCl
Soak time: 0.5～2min.
Two, the brilliant nickel coating of steel band two sides direct current electrode position micron, promptly inside and outside bottom
Plating bath is formed: NiSO
47H
2O 250～300g/L
NiCl
2·6H
2O 30～50g/L
Boric acid 30～50g/L
Direct current electrode position technological parameter: current density: 3～6A/dm
2
PH value: 3.5～4.5
Temperature: 40～60 ℃;
Anode: nickel plate.
Three, diffusion annealing
With electroplating 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 2～12 hours.
Four, a lateral vein of steel band formation battery container outer surface is the nickel coating of 50～100nm, i.e. outer middle layer towards electroplating crystallite dimension
Plating bath is formed: NiSO
47H
2O 250～300g/L
NiCl
2·6H
2O 30～50g/L
Boric acid 30～50g/L
Cumarin 0.05～0.15g/L
Formaldehyde 0.2～0.3ml/L
Pulse plating technological parameter: average current density: 3～6A/dm
2
PH value: 3.5～4.5
i
on： 5～50ms
i
off： 5～250ms
Temperature: 40～60 ℃
Anode: nickel plate.
Five, a lateral vein of steel band formation battery container inner surface dashes to electroplate and contains the nano wire nickel composite film, promptly interior intermediate layer
1. contain the preparation of the nickel composite deposite plating bath of nano wire: 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 small amount of 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 to add diameter be 20～40nm, length is nano wire and the softex kw of 0.5～1 μ m; Behind ultrasonic stirring 30min, obtain containing the nickel composite deposite plating bath of suspension nano wire, said nano wire is prepared from through anodic oxidation aluminium formwork electro-deposition (AAO);
2. contain the preparation of the nickel composite deposite of nano wire: with the 1. the nickel composite deposite plating bath that contains the suspension nano wire that obtains of step put into and be with hyperacoustic water bath with thermostatic control; And carry out ultrasonic agitation, and put into the composite deposite plating bath to the steel band of process operation in early stage then, connect the negative pole of power supply; Positive pole connects the nickel plate; Carry out composite plating, up to the nickel composite deposite that contains nano wire that obtains desired thickness, outage finishes;
The nickel composite film plating bath that contains the suspension 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;
Nano wire 1-5g/L;
Softex kw 1.4-4.2 * 10
-3Mol (g nano wire)
-1
The pulse plating technological parameter:
Average current density 3～5A/dm
2
i
on 5～50ms；；
i
off 5～250ms；
Ultrasonic stirring frequency 40～60Hz;
Ultrasonic stirring power 200～400W.
40～70 ℃ of temperature;
PH value 3.5～5.5;
Anode nickel plates.
Six, steel band two sides impulse jet is electroplated nickel-cobalt alloy layer, promptly inside and outside top layer
Plating bath is formed: NiSO
47H
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
Impulse jet electroplating technological parameter: peak current density: 47～82A/dm
2
Duty ratio: 15～25%
Plating bath spray speed: 1000～1500L/h
Temperature: 55～65 ℃
PH value: 2.5～3.5
Anode: nickel-cobalt alloy pipe.
Seven, cleaning, drying
The steel band of the equal plating multilayer coating in both sides is used distilled water flushing, then oven dry.
Eight, insulation dehydrogenation
The steel band that plating is good places and is incubated under 150～200 ℃ of conditions, to remove the hydrogen that in electroplating process, produces in the coating.
Below respectively go on foot the thickness of electroplating time decision coating.
Plating as battery case of the present invention has the steel band of the MULTILAYER COMPOSITE coating that contains nano wire; Comprehensive alkaline Mn cell is to the performance requirement of battery container each side; Adopt multi-layer film structure (being the multilayer coating structure), the adhesion that has case hardness height, coating and substrate simultaneously is good, internal resistance is little, be difficult for efflorescence, the alkali corrosion resistance performance is good.Multilayer film has been adopted the gradient distribution design of hardness, made between coating and the substrate, hardness number is mated each other between coating and the coating.In addition, owing to the inventor has carried out limiting effectively making material of the present invention demonstrate the character that obviously is different from the conventional monolayers material aspect the decay resistance of mechanics, electricity, magnetics and material with the crystallite dimension that constitutes coating to the thickness of the coating of each layer.Special, constitute at steel band the battery container inner surface a side surface plating one deck contain nano wire nickel composite film as interior intermediate layer, can in the case hardness that does not reduce the battery container inwall, strengthen the toughness of coating.
The nano wire of using among the present invention can be nickel nano wire, cobalt nanowire, bismuth nano-wire etc., and wherein preferred bismuth nano-wire because the alkali corrosion resistance performance of bismuth is best, can not dissolve for a long time with after alkaline electrolyte contacts.Because steel band top layer coating requires to have higher hardness, thus the high metal or alloy coating of hardness generally adopted, and adopt a series of technology to make prepared top layer coating have less crystallite dimension, coating is fine and close.Yet such coating often has higher internal stress, can reduce the toughness of coating, causes brittle coating.Generally, along with reducing of size, nano wire can embody than the better mechanical performance of massive material, and toughness improves.Compound with metal nanometer line in the nickel coating in coating intermediate layer, can under the prerequisite that does not reduce the multilayer coating case hardness, improve ductility of electrodeposited film, improve the punching performance of coating.
Be plated on steel band and be prepared from through the impulse jet electroplating technique corresponding to the nanocrystalline nickel-cobalt alloy coating on the top layer, both sides that forms the inside and outside wall of battery container, have higher hardness, its crystallite dimension is 20～50nm, and thickness is 0.1～1 μ m.Because the hardness ratio on top layer is bigger, has reduced powder phenomenon-tion and the surface tear in the punching course, and stamping forming the time, its good lubricant keeps performance can reduce frictional resistance, is convenient to the streamline production and processing, makes the efficient of punching press improve.In addition; Top layer nanoscale nickel-cobalt alloy coating has improved the decay resistance of steel band; Nano level coating with crystallite dimension that the present invention requires; Obtained higher corrosion resistance, characteristics such as coating has surfacing, densification, porosity is low, crystal grain is tiny, hardness is high, conductance is better.Be applied in the inner surface of battery container to the nanocrystalline nickel-cobalt alloy coating that possesses these characteristics, can obviously improve Corrosion Protection, electrical property and the powder performance of battery container; Be applied to the outer surface of battery container, can reduce coefficient of friction, more help battery container smooth and easy production in the battery assembling line.Because the formation of corrosion surface passivating film receives diffusion control, the Elements Diffusion speed of the nanocrystalline coating surface of top layer nickel-cobalt alloy of the present invention is higher than the brilliant coating of micron, so the corrosion resistance of nanocrystalline coating is higher than the brilliant coating of micron.And along with the reduction of coating crystallite dimension, the corrosion resistance of coating raises.In addition, passivation reaction starts from the lattice defect of coating surface, and the nanocrystalline coating of nickel-cobalt alloy on top layer, steel band both sides has the crystal boundary and the dislocation of higher density.Therefore, nickel-cobalt alloy nanocrystalline coating in top layer, steel band both sides has the passivating film nucleating point of higher density, thereby makes nanocrystalline coating have high-quality passivating film and lower corrosion rate.
Description of drawings
Fig. 1 is a coating structure sketch map of the present invention, and 1 is substrate among the figure, and 2 is outer bottom, and 3 is outer middle layer, and 4 is extexine, and 5 is interior bottom, and 6 is interior intermediate layer, and 7 is the endosexine;
Fig. 2 is a process chart of the present invention.
Embodiment
Following examples are intended to explain the present invention rather than to further qualification of the present invention.
Steel band of the present invention is to be substrate 1 with the steel band, steel band corresponding to the one side of battery container outer surface on the brilliant nickel coating of plating one deck micron as outside bottom 2, the coating crystallite dimension is 0.1～0.5 μ m, thickness is 0.5～2.0 μ m; Plating one deck nano-crystal nickel coating is as outer middle layer 3, and the crystallite dimension of coating is 50～100nm, and thickness is 1～2 μ m; The nanocrystalline nickel-cobalt alloy coating of plating one deck is as extexine 4, and crystallite dimension is 20～50nm, and thickness is 0.1～1 μ m; Steel band corresponding to a side surface of battery container inner surface on the brilliant nickel coating of plating one deck micron as interior bottom 5, the coating crystallite dimension is 0.1～0.5 μ m, thickness is 0.5～2.0 μ m; Plating one deck contains the nickel composite film of nano wire as interior intermediate layer 6, and the crystallite dimension of coating is 50～100nm, and thickness is 0.5～1.5 μ m; The nanocrystalline nickel-cobalt alloy coating of plating one deck is as endosexine 7, and the coating crystallite dimension is 20～50nm, and thickness is 0.1～1 μ m.(see figure 1)
Embodiment
The concrete preparation process (see figure 2) of above-mentioned steel band: the thickness of selecting Shanghai Baosteel production for use is that the BDCK battery special steel strip of 0.25mm is as electroplated substrates.Its chemical composition is: C:0.029% (% representes percetage by weight, down together)
Si：0.02％
Mn：0.2％
P：0.09％
S：0.003％
Al：0.06％。
One, mild-carbon steel strip is plated pre-treatment
In order to make coating and substrate that good binding arranged, must the target substrate carry out careful surface preparation before electroplating.Because the surface of used mild-carbon steel strip is more smooth, need not polish and mechanical polishing before the nickel plating, directly carries out oil removing and activation processing.Adopt chemical high temperature deoiling method, after the oil removing fully, specimen surface is rinsed well, put into activator then and carry out activation with distilled water.The taking-up sample is electroplated after cleaning with distilled water once more at last immediately.
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 carry out activation with distilled water.
Activator is formed: 3vol%HCl
Soak time: 1min.
Two, the brilliant nickel coating of two-sided direct current electrode position micron
Plating bath is formed: NiSO
47H
2O 280g/L
NiCl
2·6H
2O 40g/L
Boric acid 40g/L
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.
Three, diffusion annealing
With electroplating 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 600 ℃, annealing time 3 hours.
Four, a lateral vein of steel band formation battery container outer surface is towards the brilliant nickel coating of electroplating nano
Plating bath is formed: NiSO
47H
2O 280g/L
NiCl
2·6H
2O 40g/L
Boric acid 40g/L
Cumarin 0.1g/L
Formaldehyde 0.25ml/L;
Pulse plating technological parameter: average current density: 4A/dm
2
PH value: 4
i
on： 30ms
i
off： 120ms
Temperature: 50 ℃
Anode: nickel plate
Time: 60s
Under these conditions, preparing crystallite dimension is 50～100nm, and thickness is the nickel coating of 0.8 μ m.
Five, a lateral vein of steel band formation battery container inner surface dashes to electroplate and contains the nano wire nickel composite film
Said nano wire is 20～40nm for the diameter that uses the alumina formwork method to form, and length is the bismuth nano-wire of 0.5～1 μ m.
(1) contains the preparation of the nickel composite deposite plating bath of bismuth nano-wire: 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 small amount of 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 bismuth nano-wire and the softex kw of 0.5～1 μ m, behind ultrasonic stirring 30min, obtains containing the nickel composite deposite plating bath of suspension bismuth nano-wire;
(2) contain the preparation of the nickel composite deposite of bismuth nano-wire: with the 1. the nickel composite deposite plating bath that contains the suspension bismuth nano-wire that obtains of step put into and be with hyperacoustic water bath with thermostatic control (60 ℃ of thermostat temperatures); And carry out ultrasonic agitation, and put into the composite deposite plating bath to the steel band of process operation in early stage then, connect the negative pole of power supply; Positive pole connects the nickel plate; Carry out composite plating, up to the nickel composite deposite that contains bismuth nano-wire that obtains desired thickness, outage finishes.
The nickel composite film plating bath that contains the suspension bismuth nano-wire is formed:
NiSO
4·7H
2O 250g/L
NiCl
2·6H
2O 50g/L
H
3BO
3 35g/L
Saccharin sodium 1.0-1.5g/L
Bismuth 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
Ultrasonic stirring frequency 50Hz
Ultrasonic stirring power 300W
60 ℃ of temperature
PH value 4.5
Anode nickel plates
Time: 30s
Under these conditions, preparing one deck crystallite dimension is 50～100nm, and thickness is the nickel composite film coating that contains the suspension bismuth nano-wire of 0.5 μ m.
Six, the brilliant nickel-cobalt alloy layer of two-sided impulse jet electroplating nano
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
Duty ratio: 20%
Plating bath spray speed: 1400L/h
Temperature: 60 ℃
PH value: 3
Anode: nickel-cobalt alloy pipe
Electroplating time: 10s
Under these conditions, it is 20～50nm that crystallite dimension is prepared in the steel band both sides, and thickness is the nanocrystalline nickel-cobalt alloy coating of 0.5 μ m.
Seven, cleaning, drying
The steel band of the equal plating multilayer coating in both sides is clean with distilled water flushing, oven dry then.
Eight, insulation dehydrogenation
The steel band that plating is good places and is incubated under 200 ℃ of conditions, to remove the hydrogen that in electroplating process, produces in the coating.
Present embodiment steel band coating crystallite dimension is through measuring with Japanese D/MAX-RB X-ray diffraction appearance of science, calculating according to the Scherrer formula.
The thickness of coating of present embodiment steel band measures through the Alpha-Step IQ step appearance that U.S. KLA Tencor company produces.
The coating surface hardness of present embodiment steel band measures through the HV-1000 micro Vickers.
Performance test
Produce sample in the following manner, as 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 following:
Plating bath comprises: NiSO
47H
2O 280g/L
NiCl
2·6H
2O 40g/L
Boric acid 40g/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 strikes out battery case, with identical preparation method and prescription assembling LR6 alkaline battery, makes the contrast test of battery performance then.Following table 1 is finished product battery performance test comparative analysis report.
Table 1 is finished product battery performance test comparative analysis report.
Claims (8)
1. a plating contains the steel band of the multi-layer compound film of nano wire; It is characterized in that; With the steel band is substrate (1), steel band corresponding to the one side of battery container outer surface on plating one deck crystallite dimension be 0.1～0.5 μ m, thickness is that the brilliant nickel coating of micron of 0.5～2.0 μ m is as outer bottom (2); Plating one deck crystallite dimension is 50～100nm, and thickness is that the nano-crystal nickel coating of 0.5～1.5 μ m is as outer middle layer (3); Plating one deck crystallite dimension is 20～50nm, and thickness is that the nanocrystalline nickel-cobalt alloy coating of 0.1～1 μ m is as extexine (4); Steel band corresponding to a side surface of battery container inner surface on plating one deck crystallite dimension be 0.1～0.5 μ m, thickness be 0.5～2.0 μ m the micron brilliant nickel coating as interior bottom (5); Plating one deck crystallite dimension is 50～100nm, and thickness is that the nickel composite film that contains nano wire of 0.5～1.5 μ m is as interior intermediate layer (6); Plating one deck crystallite dimension is 20～50nm, and thickness is that the nanocrystalline nickel-cobalt alloy coating of 0.1～1 μ m is as endosexine (7);
Described nano wire is one or more in nickel nano wire, cobalt nanowire, the bismuth nano-wire;
Inside and outside bottom prepares through the mode of direct current electrode position;
Inside and outside intermediate layer prepares through the mode of pulse plating;
The mode that electroplate through impulse jet on inside and outside top layer prepares.
2. steel band according to claim 1 is characterized in that, described nano wire is a bismuth nano-wire.
3. steel band according to claim 1 is characterized in that, the content of nano wire is 0.5～5wt% in the described nickel composite deposite that contains nano wire.
4. according to claim 1 or 3 described steel bands, it is characterized in that the content of nano wire is 2wt% in the described nickel composite deposite that contains nano wire.
5. according to claim 1 or 3 described steel bands, it is characterized in that described nanowire diameter is 20～40nm, length is 0.5～1 μ m.
6. steel band according to claim 1 is characterized in that, the cobalt content of described extexine (4) and endosexine (7) is 0.5～5wt%.
7. according to claim 1 or 6 described steel bands, it is characterized in that the cobalt content of described extexine (4) and endosexine (7) is 2wt%.
8. the preparation method of the described steel band of claim 1 is characterized in that: may further comprise the steps:
[1] steel band plating pre-treatment;
[2] outer bottom (2) of steel band two sides direct current electrode position and interior bottom (5)
Plating bath is formed: NiSO
47H
2O 250～300g/L;
NiCl
2·6H
2O 30～50g/L；
Boric acid 30～50g/L;
Direct current electrode position technological parameter: current density: 3～6A/dm
2
PH value: 3.5～4.5;
Temperature: 40～60 ℃;
Anode: nickel plate;
[3] diffusion annealing
Steel band after will electroplating through [2] step is at 25%N
2+ 75%H
2Annealing in process under the protective atmosphere, annealing temperature are 200～750 ℃, annealing time 2～12 hours;
[4] pulse plating outer middle layer (3)
Plating bath is formed: NiSO
47H
2O 250～300g/L;
NiCl
2·6H
2O 30～50g/L；
Boric acid 30～50g/L;
Cumarin 0.05～0.15g/L;
Formaldehyde 0.2～0.3ml/L;
Pulse plating technological parameter: average current density: 3～6A/dm
2
PH value: 3.5～4.5;
i
on：5～50ms；
i
off：5～250ms；
Temperature: 40～60 ℃;
Anode: nickel plate;
[5] intermediate layer (6) in the pulse plating;
Described [5] step may further comprise the steps and condition:
1. contain the preparation of the nickel composite film plating bath of nano wire: 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 nano wire and the softex kw of 0.5～1 μ m, behind ultrasonic stirring 30min, obtains containing the nickel composite deposite plating bath of suspension nano wire;
2. contain the preparation of the nickel composite film of nano wire: with the 1. the nickel composite deposite plating bath that contains the suspension nano wire that obtains of step put into and be with hyperacoustic 60 ℃ of waters bath with thermostatic control; And carry out ultrasonic agitation, and put into the composite deposite plating bath to the steel band of handling through [4] step then, connect the negative pole of power supply; Positive pole connects the nickel plate; Carry out pulse plating, up to the nickel composite deposite that contains nano wire that obtains desired thickness, outage finishes;
The nickel composite film plating bath that contains the suspension nano wire is formed:
NiSO
4·7H
2O 200～300g/L；
NiCl
2·6H
2O 40～60g/L；
Boric acid 30～40g/L;
Saccharin sodium 1.0-1.5g/L;
Nano wire 1-5g/L;
Softex kw 1.4-4.2 * 10
-3Mol (g nano wire)
-1
The pulse plating technological parameter:
Average current density 3～5A/dm
2
i
on 5～50ms；；
i
off 5～250ms；
Ultrasonic stirring frequency 40～60Hz;
Ultrasonic stirring power 200～400W;
40～70 ℃ of temperature;
PH value 3.5～5.5;
Anode nickel plates;
[6] impulse jet is electroplated extexine (4) and endosexine (7)
Plating bath is formed: NiSO
47H
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
Duty ratio: 15～25%;
Plating bath spray speed: 1000～1500L/h;
Temperature: 55～65 ℃;
PH value: 2.5～3.5;
Anode: nickel-cobalt alloy pipe;
[7] cleaning, drying
The steel band of the equal plating multilayer coating in both sides is clean with distilled water flushing, oven dry then;
[8] insulation dehydrogenation
The steel band that plating is good places and is incubated under 150～200 ℃ of conditions, to remove the hydrogen that in electroplating process, produces in the coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010110129XA CN101958404B (en) | 2010-02-10 | 2010-02-10 | Nanowire-containing multilayer composite thin film plated steel belt and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010110129XA CN101958404B (en) | 2010-02-10 | 2010-02-10 | Nanowire-containing multilayer composite thin film plated steel belt and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101958404A CN101958404A (en) | 2011-01-26 |
| CN101958404B true CN101958404B (en) | 2012-07-11 |
Family
ID=43485622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010110129XA Active CN101958404B (en) | 2010-02-10 | 2010-02-10 | Nanowire-containing multilayer composite thin film plated steel belt and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101958404B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230200A (en) * | 2011-06-10 | 2011-11-02 | 湘潭大学 | Cobalt-containing nickel plated steel strip serving as lithium battery shell material and preparation method thereof |
| 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 |
| CN109301094B (en) * | 2017-07-25 | 2024-05-31 | 宁波堇山新材料有限公司 | Ni-plated steel strip, battery steel shell using same and preparation method of steel shell |
| CN115786913B (en) * | 2023-02-06 | 2023-06-06 | 江苏东方九天新能源材料有限公司 | Battery steel shell with surface plated with metal layer and processing technology thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN201626156U (en) * | 2010-02-10 | 2010-11-10 | 湘潭大学 | Steel strip plated with multiple layers of composite films containing nanowires |
Family Cites Families (2)
| 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 |
-
2010
- 2010-02-10 CN CN201010110129XA patent/CN101958404B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN201626156U (en) * | 2010-02-10 | 2010-11-10 | 湘潭大学 | Steel strip plated with multiple layers of composite films containing nanowires |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2006-093096A 2006.04.06 |
| 戴翠英，等.脉冲喷射电沉积纳米晶镍镀层的工艺优化.《湘潭大学自然科学学报》.2008,第30卷(第4期),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101958404A (en) | 2011-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102148339B (en) | Nickel-cobalt/nickel/nickel-cobalt multilayer film plated battery shell steel strip and preparation method thereof | |
| CN101954763B (en) | Nickeliferous nanowire laminated film plated steel belt and production method thereof | |
| CN102009504B (en) | Steel strip plated with multi-layer micron/nano-crystal nickel films and preparation method thereof | |
| JP6155327B2 (en) | All solid state secondary battery | |
| 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 | |
| CN101092718B (en) | Composite material of foamed metal, and preparation method | |
| JP6117099B2 (en) | Surface-treated steel sheet for battery container and manufacturing method thereof, battery container and battery | |
| Shan et al. | Amorphous Ni–S–Mn alloy as hydrogen evolution reaction cathode in alkaline medium | |
| CN102230200A (en) | Cobalt-containing nickel plated steel strip serving as lithium battery shell material and preparation method thereof | |
| CN105063685B (en) | A kind of nickel plating copper material of nickel and cobalt containing alloy layer and its preparation method and application | |
| CN105063699A (en) | Nickel-plated copper material and preparation method and application thereof | |
| CN101958404B (en) | Nanowire-containing multilayer composite thin film plated steel belt and preparation method thereof | |
| KR20140068114A (en) | Steel foil and method for producing same | |
| CN108823622A (en) | A kind of negative lug material and its manufacturing method for lithium battery | |
| CN108923024B (en) | Magnetic lithium metal battery copper-magnetic composite electrode material, and preparation process and application thereof | |
| CN101954762B (en) | Steel strip plated with composite film containing cobalt nanowires and preparation method thereof | |
| CN106848198B (en) | A kind of preparation method of lithium battery cathode pole piece | |
| JP5102945B2 (en) | Plated steel sheet for battery container, battery container using the plated steel sheet for battery container, and alkaline battery using the battery container | |
| CN201626156U (en) | Steel strip plated with multiple layers of composite films containing nanowires | |
| CN201619267U (en) | Steel strip coated with composite films containing nickel nanowires | |
| 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 | |
| CN101958405B (en) | Cobalt-containing nanowire-plated multi-layer composite thin film steel belt for battery shell and preparation method thereof | |
| CN201613679U (en) | Micrometer/nanometer crystalline nickel multilayered film planted steel band | |
| CN201616461U (en) | Cobalt-containing nanowire composite film plated steel band |
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 |
Effective date of registration: 20230809 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 |
|
| TR01 | Transfer of patent right |