CN201616462U - Steel belt used as battery casing and plated with multilayer laminated film containing cobalt nanowires - Google Patents
Steel belt used as battery casing and plated with multilayer laminated film containing cobalt nanowires Download PDFInfo
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- CN201616462U CN201616462U CN2010201142473U CN201020114247U CN201616462U CN 201616462 U CN201616462 U CN 201616462U CN 2010201142473 U CN2010201142473 U CN 2010201142473U CN 201020114247 U CN201020114247 U CN 201020114247U CN 201616462 U CN201616462 U CN 201616462U
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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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- Y02E60/10—Energy storage using batteries
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Abstract
The utility model discloses a steel belt used as a battery casing and plated with a multilayer laminated film containing cobalt nanowires. The steel belt is particularly used as the casing material for batteries, such as alkaline mercury-free batteries, lithium ion batteries, nickel-metal hydride batteries and the like, and can be used in the chemical industry, electron, packaging, magnetic materials and other fields. The utility model takes the steel strip as the base, and two surfaces of the steel strip are respectively plated with multilayer films; in the multilayer film plated on one side of the steel strip, which corresponds to the outer surface of the battery casing, the outer bottom layer is a nanocrystalline nickel-cobalt alloy plating layer with the thickness of 0.1-1.0 Mum, the outer middle layer is nanocrystalline nickel plating layer with the thickness of 0.5-2 Mum, and the outer surface layer is a nanocrystalline nickel-cobalt alloy plating layer with the thickness of 0.1-0.5 Mum; and in the multilayer film plated on the other side of the steel strip, which corresponds to the inner surface of the battery casing, the inner bottom player is a nanocrystalline nickel-cobalt alloy plating layer with the thickness of 0.1-1.0 Mum, the inner middle layer is nanocrystalline nickel plating layer with the thickness of 0.5-2 Mum, and the inner surface layer is a nanocrystalline nickel-cobalt alloy plating layer with the thickness of 0.1-1.0 Mum. The steel strip manufactured by the utility model has excellent corrosion resistance and punching resistance.
Description
Technical field
The utility model relates to the steel band 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 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.
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 by 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 by finishing procedure by 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 and disclose a kind of plating nickel-cobalt alloy coating in the flat 10-152522 communique, battery container steel band of perhaps first nickel plating nickel plating again-cobalt alloy coating and preparation method thereof.Because the hardness height of nickel-cobalt alloy when punch process, easily generates very thin crackle in the coating, 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 is adopted a series of technology to make prepared 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.
The utility model content
The purpose of this utility model be to provide a kind of be used for battery container steel band, it has excellent corrosion resisting performance and punching performance.
A kind of plating as battery case of the present utility model contains the steel band of the multi-layer compound film of cobalt nanowire, is substrate with the steel band, at steel band two sides difference plating multilayer film; 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 described multi-layer compound film is 0.5～5wt%.Be preferably 2wt%.
Plating as battery case described in the utility model has the steel band of the multi-layer compound film that contains cobalt nanowire, adopted multi-layer film structure (being the multilayer coating structure), has 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 utility model 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 to the thickness of each layer film and the crystallite dimension of formation 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 utility model (being inside and outside bottom) forms by 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 the utility model nickel-cobalt alloy coating 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 utility model (being inside and outside intermediate layer) forms by 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 utility model (being extexine) is prepared from by 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 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, easy inner surface at battery case forms trickle crackle, and 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 utility model also has characteristics such as surfacing, densification, porosity be low, makes nanocrystalline nickel-cobalt alloy coating have excellent corrosion resisting performance.Its mechanism is as follows: on the one hand, because the formation of corrosion surface passivating film is subjected to 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 by pulse plating is prepared from finite concentration.Described cobalt nanowire is prepared from by 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 utility model design contains the nickel composite deposite of nano wire, has higher ductility of electrodeposited film, also has superior corrosion resistance energy 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 utility model adopted has remedied shortcoming separately again mutually in the advantage that merges each monofilm.The plating that the utility model provides 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 both sides are to make the coating structure densification for the multi-layer film structure of the brilliant coating of micron in the middle of the nanocrystalline nickel-cobalt alloy coating in the utility model, 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 of battery container and reduces surface tear; 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 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.
Embodiment
Following examples are intended to illustrate the utility model rather than to further qualification of the present utility model.
Embodiment
Plating as battery case of the present utility model contains the steel band of the multi-layer compound film of cobalt nanowire, is substrate 1 with the steel band, at steel band two sides difference plating multilayer film; 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% (% represents percetage by weight, down together)
Si：0.02％
Mn：0.2％
P：0.09％
S：0.003％
Al：0.06％
1, plating front surface preliminary treatment
In order to make coating and substrate 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, do not need polishing and mechanical polishing before the nickel plating, directly carry out oil removing and activation processing.This example adopts chemical high temperature deoiling method.
Degreasing fluid is: NaOH 70g/L
Na
2CO
3 40g/L
Na
3PO
4 25g/L
Na
2SiO
3 10g/L
Degreasing fluid temperature: 80 ℃
The oil removing time: 3min
After the oil removing fully, specimen surface is rinsed well, put into activator again and activate with distilled water.
Activator is formed: 3vol%HCl
Soak time: 1min.
2, the 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, and 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 nickel coating of 0.8 μ m.
4, steel band constitutes the brilliant nickel-cobalt alloy layer of an impulse jet electroplating nano of battery container outer surface 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 nickel-cobalt alloy coating of 0.5 μ m.
5, a pulse plating of steel band formation battery container inner surface is mixed with the nickel composite deposite of 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, obtains containing the nickel composite deposite plating bath of suspension cobalt nanowire behind ultrasonic stirring 30min;
B. contain the preparation of the nickel composite deposite of cobalt nanowire: the plating bath that contains the suspension cobalt nanowire that step a is obtained is put into and is with hyperacoustic water bath with thermostatic control, 60 ℃ of thermostat temperatures, carry out ultrasonic agitation, then steel band is put into the composite deposite plating bath, connect the negative pole of power supply, positive pole connects the nickel plate, carries out composite plating, up to obtaining thickness is the nickel composite deposite that contains cobalt nanowire of 0.1～1.0 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.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 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 (3)
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 thickness is the nanocrystalline nickel-cobalt alloy coating of 0.1～1.0 μ m at steel band corresponding to the outer bottom (2) of the multilayer film of a side plating that forms the battery container outer surface; Outer middle layer (3) is that thickness is the brilliant nickel coating of micron of 0.5～2 μ m; Extexine (4) is that thickness is the nanocrystalline nickel-cobalt alloy coating of 0.1～0.5 μ m; Is that thickness is nano-crystal nickel-drill alloy coating of 0.1～1.0 μ m at steel band corresponding to the interior bottom (5) of the multilayer film of a side plating that forms the battery container inner surface; Interior intermediate layer (6) is that thickness is the brilliant nickel coating of micron of 0.5～2 μ m; Endosexine (7) is that thickness is the nickel composite deposite that contains cobalt nanowire of 0.1～1.0 μ m.
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, the crystallite dimension of described outer bottom (2), interior bottom (5) and endosexine (7) is 50～100nm; The crystallite dimension of outer middle layer (3) and interior intermediate layer (6) is 0.2～0.5 μ m; Extexine (4) be that crystallite dimension is 20～50nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010201142473U CN201616462U (en) | 2010-02-10 | 2010-02-10 | Steel belt used as battery casing and plated with multilayer laminated film containing cobalt nanowires |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010201142473U CN201616462U (en) | 2010-02-10 | 2010-02-10 | Steel belt used as battery casing and plated with multilayer laminated film containing cobalt nanowires |
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| Publication Number | Publication Date |
|---|---|
| CN201616462U true CN201616462U (en) | 2010-10-27 |
Family
ID=43002826
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|---|---|---|---|
| CN2010201142473U Expired - Fee Related CN201616462U (en) | 2010-02-10 | 2010-02-10 | Steel belt used as battery casing and plated with multilayer laminated film containing cobalt nanowires |
Country Status (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101958405A (en) * | 2010-02-10 | 2011-01-26 | 湘潭大学 | Cobalt-containing nanowire-plated multi-layer composite thin film steel belt for battery shell and preparation method thereof |
| CN109301094A (en) * | 2017-07-25 | 2019-02-01 | 宁波堇山新材料有限公司 | A kind of plating Ni steel band uses the preparation method of the battery steel shell of the steel band and the steel shell |
-
2010
- 2010-02-10 CN CN2010201142473U patent/CN201616462U/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101958405A (en) * | 2010-02-10 | 2011-01-26 | 湘潭大学 | Cobalt-containing nanowire-plated multi-layer composite thin film steel belt for battery shell and preparation method thereof |
| CN101958405B (en) * | 2010-02-10 | 2012-08-29 | 湘潭大学 | Cobalt-containing nanowire-plated multi-layer composite thin film steel belt for battery shell and preparation method thereof |
| CN109301094A (en) * | 2017-07-25 | 2019-02-01 | 宁波堇山新材料有限公司 | A kind of plating Ni steel band uses the preparation method of the battery steel shell of the steel band and the steel shell |
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|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101027 Termination date: 20130210 |