CN1121074C - Punched steel belt for power battery plate - Google Patents
Punched steel belt for power battery plate Download PDFInfo
- Publication number
- CN1121074C CN1121074C CN00134512A CN00134512A CN1121074C CN 1121074 C CN1121074 C CN 1121074C CN 00134512 A CN00134512 A CN 00134512A CN 00134512 A CN00134512 A CN 00134512A CN 1121074 C CN1121074 C CN 1121074C
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- CN
- China
- Prior art keywords
- burr
- nickel
- steel belt
- hole
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 120
- 239000010959 steel Substances 0.000 title claims abstract description 120
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 115
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 54
- 238000000576 coating method Methods 0.000 claims description 51
- 239000011248 coating agent Substances 0.000 claims description 50
- 229910017052 cobalt Inorganic materials 0.000 claims description 22
- 239000010941 cobalt Substances 0.000 claims description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 22
- 238000007747 plating Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 238000005275 alloying Methods 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000004080 punching Methods 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims 1
- 150000002739 metals Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000007769 metal material Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 27
- 239000011149 active material Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 239000011135 tin Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 7
- DITXJPASYXFQAS-UHFFFAOYSA-N nickel;sulfamic acid Chemical compound [Ni].NS(O)(=O)=O DITXJPASYXFQAS-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 6
- VWFLTHZUCYHIEC-UHFFFAOYSA-N cobalt sulfamic acid Chemical compound [Co].S(N)(O)(=O)=O VWFLTHZUCYHIEC-UHFFFAOYSA-N 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 239000011232 storage material Substances 0.000 description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910020637 Co-Cu Inorganic materials 0.000 description 1
- 229910002440 Co–Ni Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011536 re-plating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Cell Electrode Carriers And Collectors (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The present invention provides a punched steel belt used for polar plates of power batteries. Punched holes are arranged on the belt surface, and burs are arranged on the edges of all punched holes on the belt and are distributed on both side surfaces of the punched steel belt at intervals. An electroplated layer arranged on the punched steel belt comprises nickel and metal material with better electrochemical performance than nickel. The punched steel belt used for polar plates of power batteries has the advantages that the bonding performance and the electric conductivity are greatly enhanced, and the electrochemical performance is also improved, so that the service life of a battery using the punched steel belt as a positive plate or a negative plate can be extended. Besides, the manufacturing cost of the punched steel belt is much lower than that of the existing products. As a result, the punched steel belt for polar plates of power batteries plays a positive role in realizing the industrialization of power batteries.
Description
Technical field:
The invention belongs to the battery material field, relate to a kind of battery pole plates material, especially a kind of punched steel belt for power battery plate.
Background technology:
Information, the energy and material also claim three big pillars of current social development, and energy storage material integrates information, the energy and material, and its development is changing the development process of world civilization apace.Since middle 1980s, be the appearance of the small-sized chemical energy source such as Ni-MH battery, lithium ion battery of representative with the energy storage material,, make the mankind step into communication times for the develop rapidly of mobile communication provides power.Nowadays; the chemical energy source that with the energy storage material is representative is entering in the vehicles; become the power of automobile and motorcycle etc.; the appearance of this electrokinetic cell; the obstacle of environmental pollution and energy crisis two big restriction Development of Human Civilization can not only be properly solved, and the supply structure of world energy sources can be changed thus.
The quality of electrokinetic cell performance is decided by the performance of energy storage material wherein, and more important energy storage material is exactly wherein positive electrode and a negative material in chemical cell.And as positive and negative pole plate, its performance is the positive and negative pole plate to being made of it again, to such an extent as to the charge and discharge performance of the electrokinetic cell that constitutes, Costco Wholesale etc. all have significant impact.
The perforation nickel plated steel strip is replacing foaming nickel rapidly with outstanding advantage such as its low cost, anti-high current charge-discharge, becomes the first-selected plate material of electrokinetic cell.Perforated steel ribbon has two important function in the battery manufacture process: first effect is the carrier as battery cathode or positive electrode.Requirement to it is should fill described active material as much as possible on perforated steel ribbon, and the active material on it is had stronger adhesive property.China Patent No. is ZL98241828.0, the utility model patent that name is called " perforated steel band for battery pole plate " discloses a kind of perforated steel ribbon, its increase to the loading of active material on the perforated steel ribbon has positive contribution, and its specific perforation pattern and perforation shape make the voidage of steel band be greatly improved.But its exploration to the adhesive property of perforated steel ribbon but is more superficial.A kind of general understanding is arranged in the battery electrode manufacturing: boring a hole on the perforated steel ribbon, the limit, hole is jagged to be harmful to, but in the punching course of reality, some burrs more or less always appear in the limit, hole, therefore, in the sector, just there is perforation burr (also being called peak) can not surpass the industry standard of 0.01mm.In above-mentioned patent, the inventor has realized that the existence of burr is favourable on bonding active material to perforated steel ribbon, still, does not still break away from usual idea, and the height of burr has still been made to be controlled at regulation below the 0.5mm.Make its when making as the power battery plate material to poor-performing on the more substantial active material of the general battery of ratio that will fill bonding.
Second effect of perforated steel ribbon in the battery manufacture process is the collector as battery, in charge and discharge process, plays electric action.Specific requirement is that good conductivity, internal resistance are little, and the corrosion resistance of being is arranged again.The perforated steel ribbon that above-mentioned patent provided is in conductivity and reduce aspect the internal resistance inadequately, and steel band wherein because burr is less and lower, makes the contact area of steel band and active material less when combining with active material, causes conductivity relatively poor.In addition, comprise in the prior art of aforementioned patent that the surface of perforated steel ribbon all is to be provided with one deck homogenous material electrodeposited coating, is the nickel electrodeposited coating.Nickel is the material that good anti-electrode pad corrodes, but its electrochemical properties is not well, has very high electrochemical character especially for use in this generic request of electrokinetic cell, as aspects such as very high overpotential for oxygen evolution or overpotential of hydrogen evolution, and all can not be satisfactory.
Summary of the invention:
The objective of the invention is to improve the defective of prior art, a kind of perforated steel ribbon applicable to the power battery plate of making the high charge-discharge performance is provided, it has high charge-discharge performance, and a large amount of active materials with the electrokinetic cell of its making are had very high fillibility and cementability.Further aim of the present invention is to provide a kind of have very low liberation of hydrogen or overpotential for oxygen evolution, the perforated steel ribbon that electrochemical properties is good.
The object of the present invention is achieved like this:
A kind of punched steel belt for power battery plate is banded structure, has perforation on the zone face, and limits, perforation hole all on the described steel band are provided with burr, and described burr compartment of terrain distributes on the two sides of described perforated steel ribbon; On any one side of described perforated steel ribbon, there is not burr on this side in one of them hole, on its circumference on every side described burr is being arranged on hole adjacent on the both direction at least on the same side; Wherein
The described burr that described perforated edge punching press forms is by constituting as all material in the hole of going out the hole, and the height of burr is 0.5～5mm;
Be provided with composite galvanized coating on described perforated steel ribbon surface, described composite galvanized coating is: the electrodeposited coating of bottom is the nickel electrodeposited coating, and overlay coating is: cobalt or copper or silver or palladium electrodeposited coating; Perhaps be zinc or tin or cadmium electrodeposited coating.
The present invention also provides a kind of punched steel belt for power battery plate, is banded structure, has perforation on the zone face, and limits, perforation hole all on the described steel band are provided with burr, and described burr compartment of terrain distributes on the two sides of described perforated steel ribbon; On any one side of described perforated steel ribbon, there is not burr on this side in one of them hole, on its circumference on every side described burr is being arranged on hole adjacent on the both direction at least on the same side; Wherein
The described burr that described perforated edge punching press forms is by constituting as all material in the hole of going out the hole, and the height of burr is 0.5～5mm; Be provided with alloy plated layer on described perforated steel ribbon surface, the alloying element of described alloy plated layer except nickel is cobalt or copper or silver or palladium, or a kind of, two or three mixing in them; Perhaps zinc or tin or cadmium, or a kind of, two or three mixing in them.
Punched steel belt for power battery plate provided by the invention is banded structure, has the punching press perforation on the zone face, is provided with burr with going up all limits, perforation hole, and described burr compartment of terrain distributes on the two sides of described perforated steel ribbon.
Described burr is spaced apart on two sides of perforated steel ribbon can be following rule:
On any one side of described perforated steel ribbon, there is not burr (burr is on the another side) on this side in any one hole in the middle of it, on the circumference around it described burr is arranged on hole adjacent on the both direction at least.
When the perforation on the perforated steel ribbon when being in line (about perforation of each each row of row, front and back all arrange alignedly), the burr of adjacent two rounds is located at respectively on two sides of perforated steel ribbon, i.e. burr interlacing two sides is staggered.At this moment, if a carrot-free hole on this side on the selected arbitrarily side is jagged on the adjacent hole on the both direction in this hole.
When being in line when boring a hole, the better arrangement mode of burr is: the colleague is located at the steel band both sides alternately with the burr that lists on the adjacent perforated, promptly in same eleven punch 11, the burr in adjacent two holes is located at respectively on two sides of steel band, and in the same row perforation, the burr in adjacent two holes also is located at respectively on two sides of steel band.
The arrangement mode that also has a kind of perforation, promptly wrong row: in any two eleven punch 11s, the position of one eleven punch 11 and another be the aligned in position in the gap of adjacent lines perforation with it, wrong row's perforation, burr is in same eleven punch 11 on it, the burr in adjacent two holes is located at respectively on two sides of steel band, and in the perforation of same row, the burr in adjacent two holes also is located at respectively on two sides of steel band.
Under above-mentioned in line staggered burr distribution and two kinds of situations of the staggered burr distribution of wrong row, any one is carrot-free perforation on a side, and is all jagged at the adjacent holes of this side opening on four direction around it.
The effect of burr is to improve pole plate to making the fillibility and the cementability of active material provided thereon in the battery.There is not the less perforated steel ribbon of burr or burr, it just holds active material by the perforation on it, and the porosity of perforated steel ribbon (percentage of perforation field on the unit are steel band) is if excessive, then the tensile strength of perforated steel ribbon will reduce, the mechanical property of perforated steel ribbon is reduced, so the porosity of general perforated steel ribbon is no more than 60%.Burr on the punching edge has been arranged, equal constituting the new space that holds active material again by the burr on each hole on the steel strip surface, therefore, each Kong Jieshe burr and burr distribute on two sides of steel band uniform sequentially on the perforated steel ribbon, and be highly beneficial to the fillibility of active material to improving perforated steel ribbon greatly.Simultaneously, described burr also is very favorable to the raising of the cementability that invests the active material on its steel band, by punching out, steel band pore-forming, the locational steel of pore-forming break to erect in bore edges and form burr, the edge of burr is very coarse, therefore, it is very strong to the cementability attached to the active material on the steel band, in addition, not only high but also many burrs can increase the unit are pole plate that is used for electrokinetic cell and the contact area of active material on the punched steel plate, thereby improve charging performance.Burr in the described perforation on the side, both sides of steel band evenly distribution can avoid when it makes pole plate active material by coming off on it.But if not distributing equably, also be to be, but the phenomenon of dry linting can occur in the burr more sparse place that distributes, in this case, the burr by the perforation of edge distribute answer comparatively dense some.
The height of described burr can be 0.5-5mm.
For fillibility and cementability and the conductivity that improves this perforated steel ribbon to greatest extent, when the punching out steel band is bored a hole, the metal that sweeps away is dropped, and change into burr fully is preferred plan, and promptly a described perforated edge is by constituting as all material in the hole of perforation place by the burr that punching press forms.Like this except can obtaining better fillibility and cementability and conductivity, and can improve raw-material utilance effectively.This steel band can realize that steel band both sides burr distributes uniformly by double piercing in the course of processing, also can once be washed into by establishing drift in the top and bottom of steel band.
For the perforated steel ribbon that makes power battery plate provided by the invention reduces liberation of hydrogen tolerance making when making negative pole behind the battery, when making positive pole, reduce and analyse amount of oxygen, thereby reduce the internal resistance and the self discharge tendency of battery, such electrodeposited coating is set: include the element that its chemical property is higher than nickel in the described electrodeposited coating on perforated steel ribbon, when this steel band is used as anode plate, can comprise in the electrodeposited coating that overpotential for oxygen evolution is higher than the metal of nickel, as cobalt (Co), copper (Cu), silver (Ag), or palladium (Pd) etc., when this steel band is used as negative plates, can comprise in the electrodeposited coating that overpotential of hydrogen evolution is higher than the metal of nickel, as zinc (Zn), tin (Sn) or cadmium (Gd).
Wherein a kind of scheme is: establish nickel coating on perforated steel ribbon, on described nickel dam re-plating one its electrochemistry is set can better the coat of metal, during as the negative pole of battery, described metal level is its overpotential of hydrogen evolution metal level higher than nickel, as zinc layer, tin layer or cadmium layer at this steel band; During as battery anodal, described metal level is its overpotential for oxygen evolution metal level higher than nickel, as cobalt layer, copper layer or palladium layer at this steel band.The coating of establishing one of above-mentioned each metal on nickel coating all can improve the chemical property of pole plate effectively.
But, the cost of cobalt, copper, palladium or zinc, tin, cadmium all is higher than nickel, and the double layer of metal electrodeposited coating will be realized by twice plating in the course of processing, for the chemical property that improves pole plate can also adopt following more economical, easy and effect might as well scheme: on described perforated steel ribbon, establish alloy layer, comprise nickel in the described alloy layer, and include in addition in cobalt, copper, silver, palladium or zinc, tin, the cadmium at least any one, constitute alloy plated layer thus.Because other alloying element that adds in the nickel electrodeposited coating, chemical property all is better than nickel, and therefore, the chemical property of the alloy plated layer of formation also just is higher than the chemical property of simple nickel coating.This scheme is in the chemical property that improves electrodeposited coating, compare with aforesaid composite deposite scheme, good but the material usage that price is high of performance significantly reduces, so the cost of product reduces, in addition, in the implementation process of this scheme, only need can obtain the electrodeposited coating of high electrochemical performance through an electroplating work procedure, more simple and easy to do in operation.
In described electrodeposited coating was set, in two coating that form in first kind of scheme, the thickness of the nickel coating of the inside can be at 0-10 μ m, and more the selection of You Huaing is 3-5 μ m, and the thickness of the coat of metal of outside can be 0-10 μ m, and more the selection of You Huaing is 3-5 μ m.
In the scheme of element alloy coating that comes from different backgrounds and possess different abilities, make the total amount of the alloying element except that nickel in the finished product perforated steel ribbon overlay coating that obtains to account for the 8-60% of electrodeposited coating total weight, if add in the above-mentioned alloying element any one, the amount of the alloying element except that nickel can account for the 8-40% of electrodeposited coating total weight, if add any two kinds in the above-mentioned alloying element, then in finished product perforated steel ribbon overlay coating nickel with add each element total amount weight ratio be: nickel: the alloying element total amount can be 4-5: 3-4; For example, add cobalt and copper in nickel, the weight ratio of nickel, cobalt, copper can be 4-5: 1.0: 2-3.
In practical operation, in the making of composite galvanized coating, be to accelerate electroplating velocity, the proportioning of nickel-plating liquid can for:
Nickel sulfamic acid (Ni (NH
2SO
3)
2) the 200-500 grams per liter;
Nickel chloride (NiCl
26H
2O) 20-50 grams per liter;
Boric acid (H
3BO
3) the 25-45 grams per liter.
The pH value of this electroplate liquid is controlled at 3-5, and the thickness of control nickel coating is at 3-5 μ m; Plating second layer alloying element, for accelerating to electroplate, the proportioning of plating bath is:
Sulfamic acid M (Ni (NH
2SO
3)
2) the 200-500 grams per liter;
Chlorination M (NiCl
26H
2O) 20-50 grams per liter;
Boric acid (H
3BO
3) the 25-45 grams per liter.
M represents any one in the above-mentioned listed alloying element in the prescription, and the pH value of this this electroplate liquid of electroplate liquid is controlled at 3-5, and the thickness of control nickel coating is at 3-5 μ m.
In second scheme, add a kind of alloying element, in the technology of implementation and operation, in every liter of nickel plating solution, add above-mentioned any one alloying element 1.25-6.1 gram, the composition of plating bath can be:
Sulfamic acid M (Ni (NH
2SO
3)
2) the 500-600 grams per liter;
Chlorination M (NiCl
26H
2O) 10-20 grams per liter;
Boric acid (H
3BO
3) the 30-50 grams per liter;
M
N+1.25-6.1 grams per liter.
Wherein M represents the alloying element that added,
N+The chemical valence of representing this alloying element, M
N+The salt of expression M element, the pH value of this electroplate liquid is controlled at 3.8-4.5, and the temperature of electroplate liquid is controlled at 40-60 ℃.
Description of drawings:
The invention will be further described below by drawings and Examples.
Fig. 1 is the structural representation of the in line perforated steel ribbon of the in line row perforation of expression burr;
Fig. 2 is the structural representation of the wrong row's of expression in line row perforation burr perforated steel ribbon;
Fig. 3 arranges the structural representation of the wrong row's of perforation burr perforated steel ribbon for expression is wrong.
Embodiment:
Embodiment 1:
Present embodiment provides a kind of steel band 1 with perforation, as shown in Figure 1, is equipped with burr 3 in its perforation 2, and the height of burr 3 is 3.5 millimeters.Perforation 2 on it is in line arrangement, and the burr on it is wrong row.
Fig. 2 and Fig. 3 express in line and wrong also wrong row's the structure of burr of arranging of perforation of the in line burr of perforation respectively.In several structures of Fig. 1-shown in Figure 3, best to the fillibility and the cementability of active material with structure steel band shown in Figure 3.
Surperficial lining at above-mentioned steel band closes electrodeposited coating, the nickel of plated underlayer 3 μ m, and the cobalt of 5 μ m is plated on the upper strata.
The electroplate liquid of nickel plating can be:
Nickel sulfamic acid 200 grams per liters;
Nickel chloride 20 grams per liters;
Boric acid 25 grams per liters;
The pH value of this electroplate liquid is controlled at 3;
The electroplate liquid of cobalt plating can be:
Sulfamic acid cobalt 200 grams per liters;
Cobalt chloride 20 grams per liters;
Boric acid 25 grams per liters
The pH value of this electroplate liquid is controlled at 3.
The electroplate liquid of nickel plating also can be:
Nickel sulfamic acid 500 grams per liters;
Nickel chloride 50 grams per liters;
Boric acid 45 grams per liters;
The pH value of this electroplate liquid is controlled at 5;
The electroplate liquid of cobalt plating can be:
Sulfamic acid cobalt 500 grams per liters;
Cobalt chloride 50 grams per liters;
Boric acid 45 grams per liters;
The pH value of this electroplate liquid is controlled at 3.
The electroplate liquid of nickel plating can also be:
Nickel sulfamic acid 350 grams per liters;
Nickel chloride 35 grams per liters;
Boric acid 30 grams per liters.
The pH value of this electroplate liquid is controlled at 4;
The electroplate liquid of cobalt plating is:
Sulfamic acid cobalt 350 grams per liters;
Cobalt chloride 35 grams per liters;
Boric acid 30 grams per liters
The pH value of this electroplate liquid is controlled at 4.
Embodiment 2:
Present embodiment provides the wrong row of a kind of perforation 2 ｀ as shown in Figure 3 burr 3 ｀ also wrong row's perforated steel ribbon 1 ｀, and the burr on 2 ｀ that bore a hole is by constituting as all material in the hole of perforation place, not having steel cuttings to drop in the punching press pore forming process.Processing is coated with nickel-cobalt alloy coating on above-mentioned steel band.
During electroplate liquid, at first, determine the nickel plating bath that contains of a fundamental component in configuration, then, add cobalt salt in containing among the nickel plating bath according to the required cobalt amount that contains in the coating.
Containing nickel plating bath can be:
Nickel sulfamic acid (Ni (NH
2SO
3)
2) 500 grams per liters;
Nickel chloride (NiCl
26H
2O) 10 grams per liters;
Boric acid (H
3BO
3) 30 grams per liters.
The pH value of this electroplate liquid is controlled at 3.8, and the temperature of electroplate liquid is controlled at 40 ℃.
Containing nickel plating bath also can be:
Nickel sulfamic acid (Ni (NH
2SO
3)
2) 600 grams per liters;
Nickel chloride (NiCl
26H
2O) 20 grams per liters;
Boric acid (H
3BO
3) 50 grams per liters.
The pH value of this electroplate liquid is controlled at 4.5, and the temperature of electroplate liquid is controlled at 60 ℃.
Containing nickel plating bath also can be:
Nickel sulfamic acid (Ni (NH
2SO
3)
2) 550 grams per liters;
Nickel chloride (NiCl
26H
2O) 15 grams per liters;
Boric acid (H
3BO
3) 40 grams per liters.
The pH value of this electroplate liquid is controlled at 4.1, and the temperature of electroplate liquid is controlled at 50 ℃.
In above-mentioned nickel plating bath, add cobalt salt (as cobalt chloride or sulfamic acid cobalt etc.).The content of cobalt and the current density of corresponding steel band product see Table 1 in the coating that adds the amount of cobalt salt and finally obtain.
Requiring the cobalt content in the coating in the present embodiment is 8-12%, by in the table 1 as can be known, in above-mentioned nickel plating bath, add the sulfamic acid cobalt to Co
2+Content be 1.25 grams per liters.Coating is controlled at 4 μ m.
Table 1
| Co 2+Content (g/l) | 1.25 | 1.5 | 1.75 | 3.5 | 4.25 | 6.1 | ||
| Current density (A/dm 2) | 5 | 8 | 2 | 8 | 2 | 3 | 3 | 3 |
| Cobalt content in the coating (wt) | 8％ | 10％ | 12％ | 9％ | 13％ | 20％ | 25％ | 31％ |
Embodiment 3:
Go up with the alternative Ni-Co alloy layer of Ni-Co-Cu alloy layer at the perforated steel ribbon 1 ' that embodiment 2 provides, the prescription of the electroplate liquid that is adopted is:
Nickelous sulfate (NiSO
47H
2O) 80-100g/l;
Cobaltous sulfate (CoSO
45H
2O) 10-15g/l;
Copper sulphate (CuSO
45H
2O) 10-12g/l;
Ammonium citrate [(NH
4)
2HC
6H
5O
7] 1-2g/l;
Asccharin 0.5-1g/l.The PH of electroplate liquid is controlled at 3.8-4.5, and temperature is controlled at room temperature.By electroplating, on steel band, form the electrodeposited coating of 5 μ m.The weight ratio of Ni, Co, Cu is Ni: Co: Cu=4-5 in the coating: 1.0: 2-3.The current density of the product that makes can be 0.5-20A/dm
2
Method with the foregoing description can be made the perforated steel ribbon that is used to make the anode pole plate, use the same method and also can make the steel band that is used to make battery negative plate, be that used alloying element should be zinc, tin or cadmium, above-mentioned parameter also all is suitable for, at this just no longer for more embodiment.
The overpotential of hydrogen evolution of alloy plated layer of added alloying element and composition and the numerical value of overpotential for oxygen evolution are shown below by table 2 and table 3.
25 ℃ of units of table 2 overpotential for oxygen evolution: volt
| Current density A/M 2 | Ni | Co | Cu | Ag | Pd | Co-Ni alloy (Co=10%) | Co-Ni-Cu (10％-70％-20％) |
| 10 | 0.353 | 0.371 | 0.442 | 0.58 | 0.711 | 0.365 | 0.412 |
| 100 | 0.519 | 0.542 | 0.580 | 0.729 | 0.809 | 0.530 | 0.573 |
25 ℃ of units of table 3 overpotential of hydrogen evolution: volt
| Current density A/M 2 | Ni | Zn | Sn | Cd |
| 100 | 0.563 | 0.716 | 0.856 | 0.981 |
Punched steel belt for power battery plate provided by the invention is owing to be equipped with burr in all perforation, and burr is higher, the fillibility and the cementability of the active material that is attached thereto when making steel band to the manufacturing battery improve greatly, this steel band is 10 times of existing steel band to the loading of active material, even tens times, dry linting not in use.High burr has also improved the conductivity of steel band.The technology of system burr is very simple, so low cost of manufacture.The present invention has further transformed the perforated steel ribbon surface plating structure, broken through the corrosion resistance of only noting steel band in the prior art, and ignore the defective that improves its chemical property, add the chemical property better material therein, to improve the chemical property of this steel band in battery, help extending the life of a cell.The characteristics of electrokinetic cell are to use power big, general monomer is more than 10Ah, require fast charging and discharging during use, and necessary high power charging-discharging uses this steel band, because its resistance is little, good conductivity, the intensity height discharges and recharges Shi Buhui at high magnification (more than 20 times) and the heating phenomenon occurs, also can not influence the life-span and the serviceability of battery.Can electrokinetic cell realize that industrialization depends mainly on its cost, reducing its manufacturing cost is the key factor that realizes the electrokinetic cell industrialization, perforated steel ribbon provided by the invention only is 1/10 of an existing foaming nickel plate material as the price of plate material, being 1/3 of existing perforation nickel plated steel strip, is 1/3 of existing perforation nickel strap.Adopt the pole plate of this steel band system battery, can make battery cost reduce more than 5%.
Claims (7)
1, a kind of punched steel belt for power battery plate is banded structure, has perforation on the zone face, and limits, perforation hole all on the described steel band are provided with burr, and described burr compartment of terrain distributes on the two sides of described perforated steel ribbon; On any one side of described perforated steel ribbon, there is not burr on this side in one of them hole, on its circumference on every side described burr is being arranged on hole adjacent on the both direction at least on the same side; It is characterized in that:
The described burr that described perforated edge punching press forms is by constituting as all material in the hole of going out the hole, and the height of burr is 0.5～5mm;
Be provided with composite galvanized coating on described perforated steel ribbon surface, described composite galvanized coating is: the electrodeposited coating of bottom is the nickel electrodeposited coating, and overlay coating is: cobalt or copper or silver or palladium electrodeposited coating; Perhaps be zinc or tin or cadmium electrodeposited coating.
2, punched steel belt for power battery plate according to claim 1 is characterized in that: in described two electrodeposited coatings that are provided with, the nickel thickness of plating layer of the inside is 3-5 μ m, and the described electrodeposition of metals of outside is 3-5 μ m.
3, a kind of punched steel belt for power battery plate is banded structure, has perforation on the zone face, and limits, perforation hole all on the described steel band are provided with burr, and described burr compartment of terrain distributes on the two sides of described perforated steel ribbon; On any one side of described perforated steel ribbon, there is not burr on this side in one of them hole, on its circumference on every side described burr is being arranged on hole adjacent on the both direction at least on the same side; It is characterized in that:
The described burr that described perforated edge punching press forms is by constituting as all material in the hole of going out the hole, and the height of burr is 0.5～5mm; Be provided with alloy plated layer on described perforated steel ribbon surface, the alloying element of described alloy plated layer except nickel is cobalt or copper or silver or palladium, or a kind of, two or three mixing in them; Perhaps zinc or tin or cadmium, or a kind of, two or three mixing in them.
4, punched steel belt for power battery plate according to claim 3 is characterized in that: the total amount of the alloying element except nickel accounts for the 8-60% of electrodeposited coating total weight.
5, punched steel belt for power battery plate according to claim 4 is characterized in that: the total amount of the alloying element except nickel accounts for the 8-40% of electrodeposited coating total weight.
6, punched steel belt for power battery plate according to claim 3 is characterized in that: add cobalt and copper in nickel, the weight ratio of nickel, cobalt, copper is 4-5: 1.0: 2-3.
7, punched steel belt for power battery plate according to claim 5 is characterized in that: described alloy plated layer is made of nickel and cobalt, and the percetage by weight of cobalt is 8-12%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00134512A CN1121074C (en) | 2000-12-08 | 2000-12-08 | Punched steel belt for power battery plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00134512A CN1121074C (en) | 2000-12-08 | 2000-12-08 | Punched steel belt for power battery plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1310487A CN1310487A (en) | 2001-08-29 |
| CN1121074C true CN1121074C (en) | 2003-09-10 |
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ID=4596246
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00134512A Expired - Lifetime CN1121074C (en) | 2000-12-08 | 2000-12-08 | Punched steel belt for power battery plate |
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|---|---|
| CN (1) | CN1121074C (en) |
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| CN102623713B (en) * | 2012-04-17 | 2015-08-12 | 河南创力新能源科技股份有限公司 | Steel-strip iron electrode and preparation method thereof |
| CN106544703A (en) * | 2016-08-10 | 2017-03-29 | 姚晓宁 | Perforation Copper Foil foil machine and its production technology |
| CN108039456A (en) * | 2017-10-19 | 2018-05-15 | 惠州时代电池有限公司 | Use for nickel-hydrogen battery positive plate |
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2000
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| Publication number | Publication date |
|---|---|
| CN1310487A (en) | 2001-08-29 |
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