CN101958405B - Cobalt-containing nanowire-plated multi-layer composite thin film steel belt for battery shell and preparation method thereof - Google Patents
Cobalt-containing nanowire-plated multi-layer composite thin film steel belt for battery shell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cobalt-containing nanowire-plated multi-layer composite thin film steel belt for a battery shell and a preparation method thereof. The steel belt is specifically a battery outer shell material applied to 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: firstly, plating a layer of nano-crystalline nickel-cobalt alloy layer on two faces of the steel belt in a pulse plating way respectively; secondly, plating a layer of micron crystalline nickel in a DC plating way; thirdly, plating a layer of nano crystalline nickel-cobalt alloy layer serving as an outer surface layer on the side, which corresponds to the outer surface of the battery shell, of the steel belt in a pulse injection plating way; and finally, plating a layer of cobalt-containing nanowire-plated nickle composite thin film serving as an inner surface layer on one side, which corresponds to the inner surface of the battery shell, of the steel belt in the pulse plating way. The steel belt prepared by the method has the advantages of good corrosion resistance and pressing resistance.
Description
Technical field
The present invention relates to the steel band and preparation method thereof that a kind of plating that is used for battery container contains the multi-layer compound film of cobalt nanowire.
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.
Chinese patent CN1600904A discloses a kind of nickel-plated deeply-draw steel strip and production method thereof; Continuous electroplating 2～3 μ m nickel films on mild-carbon steel strip; Handle through heat treatment and laser-impact; Make nickel coating and substrate 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.The shell of alkaline battery particularly.
U.S. Pat 4760002 discloses a kind of battery steel band and production method thereof, the one deck of plating one deck nickel film on mild-carbon steel strip, and then plating earlier cobalt thin film, and the process heat diffusion treatment forms the alloyed steel strip of nickeliferous-cobalt or nickel-cobalt-iron diffusion layer at last.Under equal conditions, with the battery case of this steel band deep-draw, compare with the nickel plating battery case, the memory property of alkaline Mn cell has improved 30%, and the discharge performance of battery also has raising by a relatively large margin simultaneously.The battery steel shell that its reason is to contain cobalt can effectively reduce the internal resistance of battery, and decay resistance is better.
Japanese patent laid-open 10-172521 communique, spy open in the flat 10-152522 communique and disclose a kind of plating nickel-cobalt alloy coating, battery container steel band of perhaps first nickel plating nickel plating again-cobalt alloy coating and preparation method thereof.Because the hardness of nickel-cobalt alloy is high, when punch process, be prone in the coating generate very thin crackle, cause that coating surface is uneven, roughness ratio is bigger, thereby improved and the contacting of positive electrode, improved battery performance.
Because the case hardness that steel band is had relatively high expectations is generally understood at steel strip surface plating the hardness high coat of metal or alloy layer, and adopted a series of technology to make prepared 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.
Summary of the invention
The object of the present invention is to provide a kind of be used for battery container steel band, it has excellent corrosion resisting performance and punching performance.
Another object of the present invention is to provide the preparation method of above-mentioned steel band.
The objective of the invention is to realize through following manner.
A kind of plating as battery case contains the steel band of the multi-layer compound film of cobalt nanowire, is substrate with the steel band, the difference plating multilayer film on the steel band two sides; Is that crystallite dimension is 50～100nm at steel band corresponding to the outer bottom of the multilayer film of a side plating that forms the battery container outer surface, and thickness is the nanocrystalline nickel-cobalt alloy coating of 0.1～1.0 μ m; Outer middle layer is that crystallite dimension is 0.2～0.5 μ m, and thickness is the brilliant nickel coating of micron of 0.5～2 μ m; Extexine is that crystallite dimension is 20～50nm, and thickness is the nanocrystalline nickel-cobalt alloy coating of 0.1～0.5 μ m; Is that crystallite dimension is 50～100nm at steel band corresponding to the interior bottom of the multilayer film of a side plating that forms the battery container inner surface, and thickness is the nanocrystalline nickel-cobalt alloy coating of 0.1～1.0 μ m; Interior intermediate layer is that crystallite dimension is 0.2～0.5 μ m, and thickness is the brilliant nickel coating of micron of 0.5～2 μ m; The endosexine is that crystallite dimension is 50～100nm, and thickness is the nickel composite deposite that contains cobalt nanowire of 0.1～1.0 μ m.
The cobalt nanowire diameter is 20～40nm in the described nickel composite deposite that contains cobalt nanowire, and length is 0.5～1 μ m.
Cobalt nanowire content is 0.5～5wt% in the described nickel composite deposite that contains cobalt nanowire, is preferably 2wt%.
The cobalt content of the nickel-cobalt alloy coating of outer bottom, extexine and the interior bottom of said multi-layer compound film is 0.5～5wt%.Be preferably 2wt%.
Above-mentioned plating as battery case has the preparation method of the steel band of the multi-layer compound film that contains cobalt nanowire: with the mild-carbon steel strip is substrate, and the mode through pulse plating is plating one deck nickel-cobalt alloy coating on the mild-carbon steel strip two sides; Then the mode through direct current electrode position on the steel band two sides coating surface one deck nickel coating; Constitute side surface plating one deck nickel-cobalt alloy coating of battery container outer surface at steel band through the mode of impulse jet plating; The nickel composite deposite that contains cobalt nanowire at last through the mode of pulse plating at side surface plating one deck of steel band formation battery container inner surface.The thickness of each coating is by the time decision of electroplating.
Technological process and condition that above-mentioned steel band is concrete are following:
1, 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 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, with distilled water specimen surface is rinsed well, the HCl that puts into 1～5vol% then carries out activation, and soak time 0.5～2min is for electroplating reaction provides active surface.Take out sample, clean with distilled water once more, electroplate immediately.
In the steel band both sides pulse plating nickel-cobalt alloy as inside and outside bottom:
Plating bath is formed:
NiSO
4·7H
2O 180～300g/L
NiCl
2·6H
2O 40～60g/L
CoSO
4·7H
2O 1～15g/L
Boric acid 25～35g/L
Cumarin 0.05～0.15g/L
Formaldehyde 0.2～0.3ml/L
The pulse plating technological parameter:
Average current density: 3～6A/dm2
PH value: 3.5～4.5
i
on： 5～50ms
i
off： 5～250ms
Temperature: 40～60 ℃
Anode: nickel cobalt (alloy) plate
3, direct current electrode position nickel coating in steel band both sides is formed as inside and outside intermediate layer plating bath:
NiSO
4·7H
2O 250～300g/L
NiCl
2·6H
2O 30～50g/L
Boric acid 30～50g/L
The direct current electrode position technological parameter:
Current density: 3～6A/dm
2
PH value: 3.5～4.5
Anode: nickel plate
Temperature: 40～60 ℃
4, the side surface impulse jet plating nickel-cobalt alloy layer of steel band formation battery container outer surface is formed as the extexine plating bath: NiSO
47H
2O 180～300g/L
NiCl
2·6H
2O 40～60g/L
CoSO
4·7H
2O 1～15g/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
5, steel band constitutes nickel composite deposite that a pulse plating of battery container inner surface contains cobalt nanowire as the endosexine;
A. contain the preparation of the nickel composite deposite plating bath of cobalt nanowire: take by weighing NiSO
47H
2O and NiCl
26H
2O is dissolved in the deionized water, and through magnetic agitation and heating, 60 ℃ of heating-up temperatures are dissolved mixture fully, obtain solution A; Take by weighing H
3BO
3Put into another container, add deionized water then, through magnetic agitation and heating, 60 ℃ of heating-up temperatures obtain transparent clear solutions B; Solution B is added solution A; Add saccharin sodium again, magnetic agitation 20min, and then the adding diameter is 20～40nm; Length is cobalt nanowire and the cetyl trimethyl bromination money of 0.5～1 μ m, behind ultrasonic stirring 30min, obtains containing the nickel composite deposite plating bath of suspension cobalt nanowire;
B. contain the preparation of the nickel composite deposite of cobalt nanowire: the plating bath that contains the suspension cobalt nanowire that step a is obtained is put into and is with hyperacoustic water bath with thermostatic control, and 60 ℃ of thermostat temperatures carry out ultrasonic agitation; Put into the composite deposite plating bath to steel band then; Connect the negative pole of power supply, positive pole connects the nickel plate, carries out composite plating; Up to obtaining thickness is the nickel composite deposite that contains cobalt nanowire of 0.1～1.0 μ m, and outage finishes;
The nickel composite film plating bath that contains the suspension cobalt nanowire is formed:
NiSO
4·7H
2O 200～300g/L
NiCl
2·6H
2O 40～60g/L
H
3BO
3 30～40g/L
Saccharin sodium 1.0～1.5g/L
Softex kw 1.4～4.2 * 10
-3Mol (g cobalt nanowire)
-1
The pulse plating technological parameter:
Average current density 3～5A/dm
2
i
on 5～50ms
i
off 5～250ms
Ultrasonic stirring frequency 40～60Hz
Ultrasonic stirring power 200～400W
40～70 ℃ of temperature
PH value 3.5～5.5
Anode nickel plates
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.
Plating as battery case of the present invention has the steel band of the multi-layer compound film that contains cobalt nanowire; Adopted multi-layer film structure (being the multilayer coating structure); Have higher intensity, can improve the bond strength of substrate and coating, reduce the space in the coating; Can improve the distribution of coating internal stress and crackle, thereby improve the decay resistance of material.In addition, owing to the inventor has carried out limiting effectively making material of the present invention often demonstrate the character that obviously is different from the conventional monolayers material at the aspects such as decay resistance of mechanics, electricity, magnetics and material with the crystallite dimension that constitutes film to the thickness of each layer film.Especially, constitute at steel band the battery container inner surface a side surface plating one deck contain the nickel composite film of cobalt nanowire, can when not reducing battery container inwall hardness, strengthen the toughness of coating.
Nanocrystalline nickel-cobalt alloy coating of the present invention (being inside and outside bottom) forms through the prepared of pulse plating, and its crystallite dimension is 50～100nm.Nickel-cobalt alloy the is particles filled slit of the micron-sized intergranule of base material, and form good engagement with the brilliant particle of micron of base material, so improved the adhesion between coating and the substrate.The thickness of nickel-cobalt alloy coating of the present invention is elite in the scope of 0.1～1.0 μ m; Be because when thickness of coating during less than 0.1 μ m; Nanocrystalline nickel-cobalt alloy crystal grain can not the micron-sized intergranule of fine filling base material the slit; Can not form effective engagement, cause the adhesion of coating and substrate to descend, also will cause leaking the iron rate increases; When thickness of coating during, can cause cost to increase greater than 1.0 μ m.
The brilliant nickel coating of micron of the present invention (being inside and outside intermediate layer) forms through the prepared of direct current electrode position, and this method is the preparation method of a kind of routine in the art, and its crystallite dimension is 0.2～0.5 μ m.Thickness is elite in the scope of 0.5～2 μ m, is because when nickel coating thickness during less than 0.5 μ m, can not reach anticorrosion ability preferably; When nickel coating thickness during, can cause the increase of cost greater than 2 μ m.
Nanocrystalline nickel-cobalt alloy coating of the present invention (being extexine) is prepared from through the impulse jet electroplating technique, and its crystallite dimension is 20～50nm, and thickness of coating is 0.1～0.5 μ m.Because top layer nanocrystalline nickel-cobalt alloy coating crystallite dimension is less, so case hardness is than higher.Surface hardness is higher to have following advantage: 1, can reduce the surface tear of steel band in striking out the battery steel shell process; 2, stamping forming the time, can reduce frictional resistance, make the efficient of punching press improve; 3, be convenient to battery smooth and easy flowing in assembling line, avoid the head of battery or bottom to produce scuffing; 4, be prone to form trickle crackle at the inner surface of battery case, the positive electrode material that helps battery fully contacts with box hat, reduces the contact resistance of battery.In addition, nanocrystalline nickel-cobalt alloy coating of the present invention also has characteristics such as surfacing, densification, porosity be low, makes nanocrystalline nickel-cobalt alloy coating have excellent corrosion resisting performance.Its mechanism is following: on the one hand, because the formation of corrosion surface passivating film receives diffusion control, the diffusion rate of nanocrystalline coating is higher than the brilliant coating of micron, so the corrosion resistance of nanocrystalline coating is higher than the brilliant coating of micron; On the other hand; Because passivation reaction starts from the lattice defect of coating surface; And nanocrystalline coating has the crystal boundary and the dislocation of higher density, so nanocrystalline coating has the passivating film nucleating point of higher density, makes nanocrystalline coating have high-quality passivating film and lower rate of corrosion.
The nickel composite deposite (being the endosexine) that contains cobalt nanowire is that (1～5g/L) cobalt nanowire joins in the nickel plating solution that configures, and the method through pulse plating is prepared from finite concentration.Described cobalt nanowire is prepared from anodic oxidation aluminium formwork electro-deposition (AAO), and its diameter is 20～40nm, and length is 0.5～1 μ m.Generally, along with reducing of size, nano wire can embody than the better mechanical performance of massive material, has higher intensity and toughness preferably.The present invention's design contains the nickel composite deposite of nano wire, has higher ductility of electrodeposited film, also has superior corrosion resistance ability and punching performance.The nickel composite deposite thickness that contains cobalt nanowire is preferably in the scope of 0.1 to 1.0 μ m.
To sum up analyze, the multi-layer compound film structural design that the present invention adopted has remedied shortcoming separately again each other in the advantage that merges each monofilm.Plating provided by the invention has the steel band of multi-layer compound film structure coating, possesses the excellent properties of the following aspects at least: 1, have good bonding force between coating and the steel band; 2, this in the present invention both sides are that the multi-layer film structure for the brilliant coating of micron makes coating structure fine and close in the middle of the nanocrystalline nickel-cobalt alloy coating; Porosity is low; Can effectively reduce the possibility of battery housing generation in use spot corrosion, improve the decay resistance of battery container; 3, the nickel-cobalt alloy coating of multi-layer compound film has adopted the impulse jet electroplating technology, has improved steel strip surface hardness, helps the punch forming and minimizing surface tear of battery container; 4, the nickel composite deposite that contains cobalt nanowire of multi-layer compound film, because mixing of cobalt nanowire makes ductility of electrodeposited film improve, interior wall coating difficult drop-off in punching course of battery container, and dew iron rate is lower than single nickel coating after the punching press.In addition, to be lower than single nickel coating, therefore use it for the inwall of battery container, can reduce the internal resistance of cell, improve the electrical property of battery owing to contain the nickel composite deposite resistivity of cobalt nanowire.
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.
A kind of plating as battery case of the present invention contains the steel band of the multi-layer compound film of cobalt nanowire, is substrate 1 with the steel band, the difference plating multilayer film on the steel band two sides; Is that crystallite dimension is 50～100nm at steel band corresponding to the outer bottom 2 of the multilayer film of a side plating that forms the battery container outer surface, and thickness is the nanocrystalline nickel-cobalt alloy coating of 0.1～1.0 μ m; Outer middle layer 3 is that crystallite dimension is 0.2～0.5 μ m, and thickness is the brilliant nickel coating of micron of 0.5～2 μ m; Extexine 4 is that crystallite dimension is 20～50nm, and thickness is the nanocrystalline nickel-cobalt alloy coating of 0.1～0.5 μ m; Is that crystallite dimension is 50～100nm at steel band corresponding to the interior bottom 5 of the multilayer film of a side plating that forms the battery container inner surface, and thickness is the nanocrystalline nickel-cobalt alloy coating of 0.1～1.0 μ m; Interior intermediate layer 6 is that crystallite dimension is 0.2～0.5 μ m, and thickness is the brilliant nickel coating of micron of 0.5～2 μ m; Endosexine 7 is that crystallite dimension is 50～100nm, and thickness is the nickel composite deposite that contains cobalt nanowire of 0.1～1.0 μ m.(see figure 1)
The thickness that present embodiment selects for use Shanghai Baoshan Iron & Steel Co., Ltd to produce is that the BDCK battery special steel strip of 0.25mm is as plating substrate.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％
1, plating front surface preliminary treatment
In order to make coating and substrate can be good at combining, the above-mentioned steel band of reply carries out following surface preparation before plating.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.This example adopts chemical high temperature deoiling method.
Degreasing fluid is: NaOH 70g/L
Na
2CO
3 40g/L
Na
3PO
4 25g/L
Na
2SiO
3 10g/L
Degreasing fluid temperature: 80 ℃
The oil removing time: 3min
After the oil removing fully, specimen surface is rinsed well, put into activator again and carry out activation with distilled water.
Activator is formed: 3vol%HCl
Soak time: 1min.
2, the nanocrystalline nickel-cobalt alloy layer of pulse plating is as inside and outside bottom
Plating bath is formed:
NiSO
4·7H
2O 200g/L
NiCl
2·6H
2O 50g/L
CoSO
4·7H
2O 5g/L
Boric acid 30g/L
Cumarin 0.1g/L
Formaldehyde 0.25ml/L
The pulse plating technological parameter:
Average current density: 5A/dm
2
PH value: 4
i
on： 30ms
i
off： 120ms
Temperature: 50 ℃
Anode: nickel cobalt (alloy) plate
Time: 30s
Under these conditions, it is 50-100nm that one deck crystallite dimension is prepared in the steel band both sides,, thickness is the nanocrystalline nickel-cobalt alloy coating of 0.5 μ m.
3, the direct current electrode position nickel coating is as inside and outside intermediate layer
Plating bath is formed:
NiSO
4·7H
2O 280g/L
NiCl
2·6H
2O 40g/L
Boric acid 40g/L
The direct current electrode position technological parameter:
Current density: 4A/dm
2
PH value: 4
Anode: nickel plate
Temperature: 50 ℃
Time: 60s
Under these conditions, it is 0.2-0.5 μ m that one deck crystallite dimension is prepared in the steel band both sides, and thickness is the brilliant nickel coating of micron of 0.8 μ m.
4, the brilliant nickel-cobalt alloy layer of an impulse jet electroplating nano of steel band formation battery container outer surface is as extexine
Plating bath is formed: NiSO
47H
2O 200g/L
NiCl
2·6H
2O 50g/L
CoSO
4·7H
2O 5g/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
Duty ratio: 20%
Plating bath spray speed: 1400L/h
Temperature: 60 ℃
PH value: 3
Anode: nickel-cobalt alloy pipe
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.
5, steel band constitutes nickel composite deposite that a pulse plating of battery container inner surface is mixed with cobalt nanowire as the endosexine
A. contain the preparation of the nickel composite deposite plating bath of cobalt nanowire: take by weighing NiSO
47H
2O and NiCl
26H
2O is dissolved in the deionized water, and through magnetic agitation and heating, 60 ℃ of heating-up temperatures are dissolved mixture fully, obtain solution A; Take by weighing H
3BO
3Put into another container, add deionized water then, through magnetic agitation and heating, 60 ℃ of heating-up temperatures obtain transparent clear solutions B; Solution B is added solution A; Add saccharin sodium again, magnetic agitation 20min, and then the adding diameter is 20～40nm; Length is cobalt nanowire and the softex kw of 0.5～1 μ m, behind ultrasonic stirring 30min, obtains containing the nickel composite deposite plating bath of suspension cobalt nanowire;
B. contain the preparation of the nickel composite deposite of cobalt nanowire: the plating bath that contains the suspension cobalt nanowire that step a is obtained is put into and is with hyperacoustic water bath with thermostatic control, and 60 ℃ of thermostat temperatures carry out ultrasonic agitation; Put into the composite deposite plating bath to steel band then; Connect the negative pole of power supply, positive pole connects the nickel plate, carries out composite plating; Up to obtaining thickness is the nickel composite deposite that contains cobalt nanowire of 0.1～1.0 μ m, and outage finishes;
The nickel composite film plating bath that contains the suspension cobalt nanowire is formed:
NiSO
4·7H
2O 250g/L
NiCl
2·6H
2O 50g/L
H
3BO
3 35g/L
Saccharin sodium 1.2g/L
Cobalt nanowire 3g/L
Softex kw 4.2 * 10
-3Mol
The pulse plating technological parameter:
Average current density 4A/dm
2
i
on 30ms
i
off 120ms
Ultrasonic stirring frequency 50Hz
Ultrasonic stirring power 300W
60 ℃ of temperature
Anode nickel plates
Time: 60s
Under these conditions, preparing one deck crystallite dimension is 50-100nm, and thickness is the nickel composite film coating that contains the suspension cobalt nanowire of 0.8 μ m.
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 200 ℃ of conditions, to remove the hydrogen that in electroplating process, produces in the coating.
The coating crystallite dimension that present embodiment is related is through measuring with Japanese D/MAX-RB X-ray diffraction appearance of science, calculating according to the Scherrer formula.
The thickness of coating that present embodiment is mentioned measures through the Alpha-Step IQ step appearance that U.S. KLA Tencor company produces.
The coating surface hardness that present embodiment is mentioned 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 finished product battery electrical property test report
Claims (10)
1. the plating as battery case contains the steel band of the multi-layer compound film of cobalt nanowire, it is characterized in that, and with the steel band substrate (1), the plating multilayer film respectively on the steel band two sides; Is that crystallite dimension is 50～100nm at steel band corresponding to the outer bottom (2) of the multilayer film of a side plating that forms the battery container outer surface, and thickness is the nanocrystalline nickel-cobalt alloy coating of 0.1～1.0 μ m; Outer middle layer (3) is that crystallite dimension is 0.2～0.5 μ m, and thickness is the brilliant nickel coating of micron of 0.5～2 μ m; Extexine (4) is that crystallite dimension is 20～50nm, and thickness is the nanocrystalline nickel-cobalt alloy coating of 0.1～0.5 μ m; Is that crystallite dimension is 50～100nm at steel band corresponding to the interior bottom (5) of the multilayer film of a side plating that forms the battery container inner surface, and thickness is the nanocrystalline nickel-cobalt alloy coating of 0.1～1.0 μ m; Interior intermediate layer (6) is that crystallite dimension is 0.2～0.5 μ m, and thickness is the brilliant nickel coating of micron of 0.5～2 μ m; Endosexine (7) is that crystallite dimension is 50～100nm, and thickness is the nickel composite deposite that contains cobalt nanowire of 0.1～1.0 μ m;
In, outer bottom prepares through the mode of pulse plating;
In, outer middle layer prepares through the mode of direct current electrode position;
The mode that extexine is electroplated through impulse jet prepares;
The endosexine prepares through the mode of pulse plating.
2. steel band according to claim 1 is characterized in that, the cobalt nanowire diameter is 20～40nm in the described nickel composite deposite that contains cobalt nanowire, and length is 0.5～1 μ m.
3. steel band according to claim 1 is characterized in that, cobalt nanowire content is 0.5～5wt% in the described nickel composite deposite that contains cobalt nanowire.
4. according to claim 1 or 2 or 3 described steel bands, it is characterized in that the content of cobalt nanowire is 2wt% in the described nickel composite deposite that contains cobalt nanowire.
5. steel band according to claim 1 is characterized in that, the cobalt content of described outer bottom (2), extexine (4) and interior bottom (5) is 0.5～5wt%.
6. according to claim 1 or 5 described steel bands, it is characterized in that the cobalt content of described outer bottom (2), extexine (4) and interior bottom (5) is 2wt%.
7. the described a kind of plating as battery case of preparation claim 1 has the steel band of the multi-layer compound film that contains cobalt nanowire; It is characterized in that; With the mild-carbon steel strip is substrate (1), and the mode through pulse plating is plating one deck nickel-cobalt alloy coating on the mild-carbon steel strip two sides; Then the mode through direct current electrode position on the steel band two sides coating surface one deck nickel coating; Constitute side surface plating one deck nickel-cobalt alloy coating of battery container outer surface at steel band through the mode of impulse jet plating; The nickel composite deposite that contains cobalt nanowire at last through the mode of pulse plating at side surface plating one deck of steel band formation battery container inner surface.
8. the preparation method of steel band according to claim 7 is characterized in that:
[1] steel band plating front surface preliminary treatment;
[2] the nanocrystalline nickel-cobalt alloy coating of pulse plating in pretreated steel band both sides
Plating bath is formed:
NiSO
4·7H
2O 180～300g/L；
NiCl
2·6H
2O 40～60g/L；
CoSO
4·7H
2O 1～15g/L；
H
3BO
3 25～35g/L；
Cumarin 0.05～0.15g/L;
Formaldehyde 0.2～0.3ml/L;
The 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 cobalt (alloy) plate;
[3] the brilliant nickel coating of direct current electrode position micron
Plating bath is formed:
NiSO
4·7H
2O 250～300g/L；
NiCl
2·6H
2O 30～50g/L；
Boric acid 30～50g/L;
The direct current electrode position technological parameter:
Current density: 3～6A/dm
2
PH value: 3.5～4.5;
Temperature: 40～60 ℃;
Anode: nickel plate;
Temperature: 40～60 ℃;
[4] steel band constitutes the brilliant nickel-cobalt alloy layer of a side surface impulse jet electroplating nano of battery container outer surface
Plating bath is formed: NiSO
47H
2O 180～300g/L;
NiCl
2·6H
2O 40～60g/L；
CoSO
4·7H
2O 1～15g/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;
PH value: 2.5～3.5;
Temperature: 55～65 ℃;
Anode: nickel-cobalt alloy pipe;
[5] a side surface pulse plating of steel band formation battery container inner surface contains the nickel composite deposite of cobalt nanowire;
[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.
9. the preparation method of steel band according to claim 8 is characterized in that, described [5] step may further comprise the steps and process conditions:
A. contain the preparation of the nickel composite deposite plating bath of cobalt nanowire: take by weighing NiSO
47H
2O and NiCl
26H
2O is dissolved in the deionized water, and through magnetic agitation and heating, 60 ℃ of heating-up temperatures are dissolved mixture fully, obtain solution A; Take by weighing H
3BO
3Put into another container, add deionized water then, through magnetic agitation and heating, 60 ℃ of heating-up temperatures obtain transparent clear solutions B; Solution B is added solution A; Add saccharin sodium again, magnetic agitation 20min, and then the adding diameter is 20～40nm; Length is cobalt nanowire and the softex kw of 0.5～1 μ m, behind ultrasonic stirring 30min, obtains containing the nickel composite deposite plating bath of suspension cobalt nanowire;
B. contain the preparation of the nickel composite deposite of cobalt nanowire: the plating bath that contains the suspension cobalt nanowire that step a is obtained is put into and is with hyperacoustic water bath with thermostatic control, and 60 ℃ of thermostat temperatures carry out ultrasonic agitation; Put into the composite deposite plating bath to steel band then; Connect the negative pole of power supply, positive pole connects the nickel plate, carries out composite plating; Up to obtaining thickness is the nickel composite deposite that contains cobalt nanowire of 0.1～1.0 μ m, and outage finishes;
The nickel composite film plating bath that contains the suspension cobalt nanowire is formed:
NiSO
4·7H
2O 200～300g/L；
NiCl
2·6H
2O 40～60g/L；
H
3BO
3 30～40g/L；
Saccharin sodium 1.0～1.5g/L;
Cobalt nanowire 1～5g/L;
Softex kw 1.4～4.2 * 10
-3Mol (g cobalt nanowire)
-1
The pulse plating technological parameter:
Average current density 3～5A/dm
2
i
on 5～50ms；
i
off 5～250ms；
Ultrasonic stirring frequency 40～60Hz;
Ultrasonic stirring power 200～400W;
40～70 ℃ of temperature;
PH value 3.5～5.5;
Anode nickel plates.
10. want the preparation method of 8 described steel bands according to right, it is characterized in that, the preliminary treatment of described plating front surface is for directly carrying out chemical high temperature 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 carry out activation with distilled water;
Activator is: 1～5vol%HCl;
Soak time: 0.5～2min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN201289867Y (en) * | 2008-10-27 | 2009-08-12 | 株洲永盛电池材料有限公司 | Single side nickel-clad stainless steel band for fastening lithium ion cell case and cover |
| CN101597780A (en) * | 2009-07-03 | 2009-12-09 | 湖南利德材料科技股份有限公司 | A kind of method for preparing the nickel-silver alloy steel strip that battery case uses |
| CN201616462U (en) * | 2010-02-10 | 2010-10-27 | 湘潭大学 | Steel belt used as battery casing and plated with multilayer laminated film containing cobalt nanowires |
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| JP2006093096A (en) * | 2004-08-23 | 2006-04-06 | Toyo Kohan Co Ltd | Plated steel sheet for battery container, battery container using same, and battery using its battery container |
| CN101384753B (en) * | 2006-02-09 | 2011-06-01 | 新日本制铁株式会社 | Tinned steel sheet excellent in corrosion resistance |
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| 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 |
| CN201616462U (en) * | 2010-02-10 | 2010-10-27 | 湘潭大学 | Steel belt used as battery casing and plated with multilayer laminated film containing cobalt nanowires |
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