CN201626156U - Steel strip plated with multiple layers of composite films containing nanowires - Google Patents
Steel strip plated with multiple layers of composite films containing nanowires Download PDFInfo
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- CN201626156U CN201626156U CN2010201141911U CN201020114191U CN201626156U CN 201626156 U CN201626156 U CN 201626156U CN 2010201141911 U CN2010201141911 U CN 2010201141911U CN 201020114191 U CN201020114191 U CN 201020114191U CN 201626156 U CN201626156 U CN 201626156U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The utility model discloses a steel strip plated with multiple layers of composite films containing nanowires, particularly relates to a material for the shells of batteries such as alkaline mercury-free batteries, lithium ion batteries, nickel-hydrogen batteries and the like, and also can be used in the fields of chemical engineering, electronic industry, packaging industry, magnetic materials and the like. The steel strip provided by the utility model serves a steel strip as a substrate; a layer of micro-grain nickel plating is plated on the steel strip on the surface corresponding to the outer surface of a battery shell to serve as an outer bottom layer with the thickness of 0.5 to 2.0 Mum; a layer of nanocrystalline nickel plating is plated to serve as an outer intermediate layer with the thickness of 0.5 to 1.5 Mum; a layer of nanocrystalline nickel-cobalt alloy plating is plated to serve as an outer surface layer with the thickness of 0.1 to 1 Mum; a layer of micro-grain nickel plating is plated on the steel strip on one side surface corresponding to the inner surface of the battery shell to serve as an inner bottom layer with the thickness of 0.5 to 2.0 Mum; a layer of nickel composite film containing nanowires is plated to serve as an inner intermediate layer with the thickness of 0.5 to 1.5 Mum; and a layer of nanocrystalline nickel-cobalt alloy plating is plated to serve as an inner surface layer with the thickness of 0.1 to 1 Mum. The steel strip provided by the utility model has favorable decay resistance and stamping performance.
Description
Technical field
The utility model relates to the steel band that a kind of plating that is used for battery container has the multi-layer compound film that contains nano wire.
Background technology
In recent years, along with people are more and more higher to the requirement of battery performance, 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 participate 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 by 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 by finishing procedure by thermal diffusion.The coating percentage 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 occurring the coating obscission easily in the punch forming process of battery container.
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 it is 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, the coating densification.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 requirement of comparison harshness 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 electrical conductivity preferably with regard to the case material that requires to make battery, and the surface hardness height.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 existing battery container steel band all is single nickel coating or duplicature design simple in structure.The shortcoming of these technology is 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 forms powder in punching course 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, occurring coating in punching course easily comes off, the coating that hardness is high often has higher internal stress in addition, 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.
The utility model content
The purpose of this utility model is to provide a kind of steel band with excellent corrosion resisting performance, punching performance of being combined closely and being formed by MULTILAYER COMPOSITE coating that contains nano wire and mild-carbon steel strip that is used for battery container.
The utility model 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, and 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 0.5～1.5 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 by 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%.
Plating as battery case described in the utility model 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 mutually between coating and the coating.In addition, owing to the inventor has carried out limiting effectively making material of the present utility model demonstrate the character that obviously is different from the conventional monolayers material aspect the decay resistance of mechanics, electricity, magnetics and material to the thickness of the coating of each layer and the crystallite dimension of formation coating.Especially, 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 in the utility model 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, the coating densification.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 by 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 utility model 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.The nanocrystalline nickel-cobalt alloy coating that possesses these characteristics is applied in the inner surface of battery container, can obviously improves 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 is subjected to DIFFUSION CONTROLLED, the Elements Diffusion speed of the nanocrystalline coating surface of top layer nickel-cobalt alloy of the present utility model 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 schematic diagram of the present utility model, 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.
The specific embodiment
Following examples are intended to illustrate the utility model rather than to further qualification of the present utility model.
Embodiment
Steel band of the present utility model 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 0.5～1.5 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)
The concrete preparation process 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% (% represents 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 be arranged, must the target substrate carry out careful 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 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 activate 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 activate 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
To 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 600 ℃, annealing time 3 hours.
Four, steel band forms a lateral vein of battery container outer surface 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 one deck crystallite dimension is 50～100nm, and thickness is the nano-crystal 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
Described nano wire is 20～40nm for the diameter that forms with the alumina formwork method, 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, obtains containing the nickel composite deposite plating bath of suspension bismuth nano-wire after ultrasonic wave stirs 30min;
(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, then the steel band of process operation in early stage is put into the composite deposite plating bath, the negative pole that connects 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 wave stirring frequency 50Hz
Ultrasonic wave power of agitator 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 deposite that contains 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;
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
Electroplating time: 10s
Under these conditions, preparing one deck crystallite dimension is 20～50nm, 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 produces in the coating in electroplating process.
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: 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 of embodiment and comparative example is struck out battery case,, make the contrast test of battery performance then with identical preparation method and prescription assembling LR6 alkaline battery.Following table 1 is finished product battery performance test comparative analysis report.
Table 1 is finished product battery performance test comparative analysis report.
Claims (5)
1. a plating contains the steel band of the multi-layer compound film of nano wire, it is characterized in that, be substrate (1) with the steel band, steel band corresponding to the one side of battery container outer surface on plating one layer thickness be 0.5～2.0 μ m the brilliant nickel coating of micron as outside bottom (2); Plating one layer thickness is that the nano-crystal nickel coating of 0.5～1.5 μ m is as outer middle layer (3); Plating one layer 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 layer thickness be 0.5～2.0 μ m the micron brilliant nickel coating as interior bottom (5); Plating one layer 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 layer thickness is that the nanocrystalline nickel-cobalt alloy coating of 0.1～1 μ m is as endosexine (7).
2. steel band according to claim 1 is characterized in that, described nano wire is one or more in nickel nano wire, cobalt nanowire, the bismuth nano-wire.
3. steel band according to claim 1 and 2 is characterized in that, described nano wire is a bismuth nano-wire.
4. steel band according to claim 1 and 2 is characterized in that, described nanowire diameter is 20～40nm, and length is 0.5～1 μ m.
5. steel band according to claim 1 is characterized in that, described outer bottom (2) is 0.1～0.5 μ m with the coating crystallite dimension of interior bottom (5); Described outer middle layer (3) is 50～100nm with the crystallite dimension of the coating in interior intermediate layer (6); Described extexine (4) is 20～50nm with the coating crystallite dimension of endosexine (7).
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| CN2010201141911U CN201626156U (en) | 2010-02-10 | 2010-02-10 | Steel strip plated with multiple layers of composite films containing nanowires |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101958404A (en) * | 2010-02-10 | 2011-01-26 | 湘潭大学 | Nanowire-containing multilayer composite thin film plated steel belt and preparation method thereof |
| CN103534389A (en) * | 2011-05-10 | 2014-01-22 | Jx日矿日石金属株式会社 | Ni-plated metal sheet, welded structure, and method for making battery material |
-
2010
- 2010-02-10 CN CN2010201141911U patent/CN201626156U/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101958404A (en) * | 2010-02-10 | 2011-01-26 | 湘潭大学 | Nanowire-containing multilayer composite thin film plated steel belt and preparation method thereof |
| CN101958404B (en) * | 2010-02-10 | 2012-07-11 | 湘潭大学 | Nanowire-containing multilayer composite thin film plated steel belt and preparation method thereof |
| CN103534389A (en) * | 2011-05-10 | 2014-01-22 | Jx日矿日石金属株式会社 | Ni-plated metal sheet, welded structure, and method for making battery material |
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