CN105525317B - Battery steel shell made from a kind of three layers of nickel plating technology of battery steel shell and the technique - Google Patents
Battery steel shell made from a kind of three layers of nickel plating technology of battery steel shell and the technique Download PDFInfo
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- CN105525317B CN105525317B CN201510965899.5A CN201510965899A CN105525317B CN 105525317 B CN105525317 B CN 105525317B CN 201510965899 A CN201510965899 A CN 201510965899A CN 105525317 B CN105525317 B CN 105525317B
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- nickel
- steel shell
- battery steel
- plating
- bright
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 390
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 195
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 95
- 239000010959 steel Substances 0.000 title claims abstract description 95
- 238000007747 plating Methods 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000005516 engineering process Methods 0.000 title claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 76
- 238000000576 coating method Methods 0.000 claims abstract description 76
- 239000011593 sulfur Substances 0.000 claims abstract description 44
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 44
- 238000009713 electroplating Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims description 38
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 14
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 14
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 14
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 13
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 claims description 5
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 claims description 5
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 4
- 229940081974 saccharin Drugs 0.000 claims description 4
- 235000019204 saccharin Nutrition 0.000 claims description 4
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 4
- SRJQTHAZUNRMPR-UYQKXTDMSA-N spinosyn A Chemical compound O([C@H]1CCC[C@@H](OC(=O)C[C@H]2[C@@H]3C=C[C@@H]4C[C@H](C[C@H]4[C@@H]3C=C2C(=O)[C@@H]1C)O[C@H]1[C@@H]([C@H](OC)[C@@H](OC)[C@H](C)O1)OC)CC)[C@H]1CC[C@H](N(C)C)[C@@H](C)O1 SRJQTHAZUNRMPR-UYQKXTDMSA-N 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 21
- 230000007797 corrosion Effects 0.000 abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 241000238097 Callinectes sapidus Species 0.000 description 10
- 239000003595 mist Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000002421 anti-septic effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 101100230509 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) hat-1 gene Proteins 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 potassium ferricyanide Chemical compound 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/16—Acetylenic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
A kind of three layers of nickel plating technology of battery steel shell, comprise the following steps：A, battery steel shell is pre-processed；B, pretreated battery steel shell surface is once electroplated, plating is covered with half light nickel coating；C, second time electroplating is carried out to the battery steel shell after step b processing, plating is covered with a high-sulfur nickel coating；D, the battery steel shell after step c processing is electroplated three times, plating is covered with a bright nickel plating layer.The invention also discloses battery steel shell made from a kind of above-mentioned technique.The present invention is by between the bright nickel plating layer of double layer nickel and half bright nickel coating, the high-sulfur plating nickel coating that strike plating last layer thickness is about 1 μm or so, due to potential difference be present between three layers of nickel, the anti-corrosion capability of half bright nickel coating in three layers of nickel system enable to great lifting, be advantageous to further delay corrosive medium to the corrosion rate of iron-based body, and significantly improve the decay resistance of coating.
Description
Technical field
The present invention relates to a kind of battery steel shell production technology, refers in particular to a kind of three layers of nickel plating technology of battery steel shell and the work
Battery steel shell made from skill.
Background technology
Aluminium alloy is the general name using aluminium as the alloy of base, and main alloy element includes copper, silicon, magnesium, zinc, manganese, minor element
Containing nickel, iron, titanium, lithium, essential element content, proportioning and impurity content in alloy have very big shadow to alloy end properties
Ring.
Battery steel shell is one of critical material for producing dry cell.The production of current battery box hat is divided into two major classes substantially,
One kind is nickel plated steel strip punch forming and then degreasing, antirust treatment, referred to as first nickel plated steel shell；Another kind is by steel strip stamping
Shaping and then degreasing, electronickelling processing, box hat is electroplated after being referred to as.In the prior art, for the barrel plating technology of rear plating box hat
The technology of last century the nineties is also maintained at present, by constantly improve, additive mode electronickelling is selected, due to battery skill
The continuous change of art, battery performance improve constantly, and service time of battery is increasingly longer, it is necessary to which the antiseptic property of battery steel shell also will
It is correspondingly improved, original nickel plated steel shell is difficult to meet the needs of high-performance, high-capacity battery.
The content of the invention
The present invention provides battery steel shell made from a kind of three layers of nickel plating technology of battery steel shell and the technique, and its main purpose exists
In overcoming the defects of existing battery steel shell is in corrosion resistance deficiency during long-term use..
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of three layers of nickel plating technology of battery steel shell, comprise the following steps：A, battery steel shell is pre-processed；B, to pre- place
Battery steel shell surface after reason is once electroplated, and plating is covered with half light nickel coating；C, to the battery after step b processing
Box hat carries out second time electroplating, and plating is covered with a high-sulfur nickel coating；D, the battery steel shell after step c processing is carried out electric three times
Plating, plating are covered with a bright nickel plating layer；The oxidizing potential of the bright nickel plating layer is less than described half bright nickel coating, the high-sulfur nickel plating
The oxidizing potential of layer is less than the bright nickel plating layer.
Further, in stepb, the once plating includes battery steel shell being placed in a semi-bright nickel technique electroplate liquid
Middle plating 100 minutes, wherein semi-bright nickel technique electroplate liquid includes：300 g/l of nickel sulfate, 50 g/l of nickel chloride, boric acid 40
G/l, 0.15 g/l of cumarin, 0.15 g/l of formaldehyde, the pH of the semi-bright nickel technique electroplate liquid is 4.0, and solution temperature is
50℃。
Further, in step c, the second time electroplating includes to put including the battery steel shell after step b processing
Electroplated 20 minutes in a high-sulfur nickel technique electroplate liquid, wherein high-sulfur nickel technique electroplate liquid includes：300 g/l of nickel sulfate, chlorination
50 g/l of nickel, 40 g/l of boric acid, 1 g/l of benzene sulfinic acid sodium salt, 0.5 g/l of butynediols, 1 g/l of saccharin, the high-sulfur nickel work
The pH of skill electroplate liquid is 2.5, and solution temperature is 50 DEG C.
Further, in step d, the battery steel shell that the plating three times is included after step c processing is placed in a light
Electroplated 60 minutes in bright nickel technique electroplate liquid, wherein bright nickel technique electroplate liquid includes：300 g/l of nickel sulfate, nickel chloride 50
G/l, 40 g/l of boric acid, the ml l of additive 10, the pH of the bright nickel technique electroplate liquid is 4.0, and solution temperature is 50 DEG C.
Further, in addition to the step e, the step e after the step d includes the battery sequentially carried out
Box hat recovery, washing, antirust treatment, this four procedure is dried, in step a, pretreatment includes the battery steel shell sequentially carried out
This four procedure is washed after degreasing, washing, pickling and acid.
A kind of battery steel shell of corrosion resistance improvement, including a box hat base material, a bright nickel plating layer, an oxidizing potential are big
It is less than the high-sulfur nickel coating of the bright nickel plating layer, institute in half bright nickel coating of the bright nickel plating layer and an oxidizing potential
The surface that half bright nickel coating is covered in the box hat base material is stated, the upper surface of the half bright nickel coating is covered with the high-sulfur
Nickel coating, the upper surface of the high-sulfur nickel coating is covered with the bright nickel plating layer.
Further, the thickness summation of described half bright nickel coating, high-sulfur nickel coating and bright nickel plating layer is 1.8 μm
~2.3 μm, the thickness of the high-sulfur nickel coating is 0.8 μm~1.2 μm.
Further, described half bright nickel coating is covered in the surface of box hat base material by one plating steps, described
Once plating includes box hat base material being placed in a semi-bright nickel technique electroplate liquid electroplating 100 minutes, wherein semi-bright nickel technique
Electroplate liquid includes：300 g/l of nickel sulfate, 50 g/l of nickel chloride, 40 g/l of boric acid, 0.15 g/l of cumarin, formaldehyde 0.15
G/l, the pH of the semi-bright nickel technique electroplate liquid is 4.0, and solution temperature is 50 DEG C.
Further, the high-sulfur nickel coating is covered in the upper table of described half bright nickel coating by a second time electroplating step
Face, the box hat base material that the second time electroplating includes will be covered with half bright nickel coating are placed in a high-sulfur nickel technique electroplate liquid and electroplated
20 minutes, wherein high-sulfur nickel technique electroplate liquid included：300 g/l of nickel sulfate, 50 g/l of nickel chloride, 40 g/l of boric acid, benzene are sub-
1 g/l of sodium sulfonate, 0.5 g/l of butynediols, 1 g/l of saccharin, the pH of the high-sulfur nickel technique electroplate liquid is 2.5, solution temperature
For 50 DEG C.
Further, the bright nickel plating layer by one three times plating step be covered in the upper table of the high-sulfur nickel coating
Face, the box hat base material that the plating three times includes will be covered with high-sulfur nickel coating are placed in a bright nickel technique electroplate liquid and electroplate 60
Minute, wherein bright nickel technique electroplate liquid includes：300 g/l of nickel sulfate, 50 g/l of nickel chloride, 40 g/l of boric acid, additive
10 ml ls, the pH of the bright nickel technique electroplate liquid is 4.0, and solution temperature is 50 DEG C.
Compared to the prior art, beneficial effect caused by the present invention is:
1st, in the present invention, by setting bright nickel plating layer and half bright nickel coating, and in the bright nickel plating of double layer nickel
Between layer and half bright nickel coating, the high-sulfur that strike plating last layer thickness is about 1 μm or so plates nickel coating, due between three layers of nickel
Potential difference be present, half bright nickel coating current potential is more than bright nickel plating layer current potential, and bright nickel plating layer current potential is more than high-sulfur nickel coating electricity
Position, thus in corrosion process, the more negative coating of current potential is preferentially corroded, so the semi-gloss in three layers of nickel system as anode
The anti-corrosion capability of bright nickel coating can arrive great lifting, be advantageous to further delay corrosion speed of the corrosive medium to iron-based body
Degree, and significantly improve the decay resistance of coating.
2nd, not only antiseptic property significantly improves the coating as made from present invention process, and equal nickel plating layer thick antiseptic property is extremely
Double less, and the electric conductivity of coating, weldability, adhesion are good, can be well adapted for meeting high-performance, high power capacity
The demand of battery.
3rd, in the present invention, compared to more conventional pure nickel plating scheme, the method can significantly improve the antiseptic property of coating, together
When the elongation percentage of coating, electric conductivity, welding performance, adhesion it is unchanged, meet the raising of battery capacity and prolonging for service life
It is long.
Brief description of the drawings
Fig. 1 is the structural representation of battery steel shell described in the embodiment of the present invention one.
Fig. 2 is the preparation flow figure of battery steel shell described in the embodiment of the present invention one.
Fig. 3 is the structural representation of battery steel shell described in the embodiment of the present invention two.
Fig. 4 is the preparation flow figure of battery steel shell described in the embodiment of the present invention two.
Fig. 5 is the rust-proof effect instance graph that battery steel shell carries out salt mist experiment in the prior art.
Fig. 6 is the rust-proof effect instance graph that battery steel shell carries out salt mist experiment described in the embodiment of the present invention one.
Fig. 7 is the rust-proof effect instance graph that battery steel shell carries out salt mist experiment described in the embodiment of the present invention two.
Fig. 8 is the rust-proof effect instance graph that battery steel shell carries out Bluepoint experiment in the prior art.
Fig. 9 is the rust-proof effect instance graph that battery steel shell carries out Bluepoint experiment described in the embodiment of the present invention one.
Figure 10 is the rust-proof effect instance graph that battery steel shell carries out Bluepoint experiment described in the embodiment of the present invention two.
Embodiment
Illustrate the embodiment of the present invention with reference to the accompanying drawings.
Embodiment one
Referring to Figures 1 and 2.A kind of battery steel shell 1 for improving corrosive nature, including a box hat base material 2 and a bright nickel plating
Layer 3, the surface of the box hat base material 2 are more than half bright nickel coating 4 of the bright nickel plating layer 3 covered with an oxidizing potential, should
The upper surface of half bright nickel coating 4 is covered with above-mentioned bright nickel plating layer 3.
Referring to Figures 1 and 2.As the preferred scheme of the present embodiment, the half bright nickel coating 4 and bright nickel plating layer 3
Thickness summation is 1.8 μm~2.3 μm.The thickness for being more highly preferred to half bright nickel coating 4 described in scheme as the present embodiment is
0.5 μm~1.5 μm.
Referring to Figures 1 and 2.The thickness of the wherein described bright nickel coating 4 of semi-gloss can be 1.2 μm, while bright nickel plating layer 3
Thickness can be 0.8 μm.
Referring to Figures 1 and 2.The preparation method of above-mentioned battery steel shell 1 is：
A kind of battery steel shell duplex nickel plating technique, comprises the following steps：
A, battery steel shell 1 is pre-processed.This step can be preferably：The pretreatment of battery steel shell 1 includes sequentially carrying out
Degreasing → washing → pickling → acid after wash this four procedure.
B, the pretreated surface of battery steel shell 1 is once electroplated, plating is covered with half light nickel coating.This step can
To be preferably：The once plating includes battery steel shell 1 being placed in a semi-bright nickel technique electroplate liquid electroplating 120 minutes, its
Middle semi-bright nickel technique electroplate liquid includes：300 g/l of nickel sulfate, 50 g/l of nickel chloride, 40 g/l of boric acid, cumarin 0.15
G/l, 0.15 g/l of formaldehyde, the pH of the semi-bright nickel technique electroplate liquid is 4.0, and solution temperature is 50 DEG C.
C, second time electroplating is carried out to the battery steel shell 1 after step b processing, plating is covered with a bright nickel coating, the light
The oxidizing potential of nickel coating 3 is less than described half bright nickel coating 4.This step can be preferably：The second time electroplating includes passing through
Battery steel shell 1 after step b processing, which is placed in a bright nickel technique electroplate liquid, electroplates 60 minutes, wherein bright nickel technique electroplate liquid
Including：300 g/l of nickel sulfate, 50 g/l of nickel chloride, 40 g/l of boric acid, the ml l of additive 10, bright nickel technique electricity
The pH of plating solution is 4.0, and solution temperature is 50 DEG C.
D, battery steel shell 1 is sequentially carried out reclaiming → wash → antirust treatment → and dries this four procedure.
In the present embodiment, it is then electric again by plating the semi-bright nickel coating of one layer of not sulfur-bearing on present battery steel shell 1
Plate the bright coating of one layer of sulfur-bearing.Because the bright nickel current potential of sulfur-bearing is relatively negative, between bright nickel and semi-bright nickel, current potential is produced
Difference, form corrosion galvanic cell, the higher bright nickel of sulfur-bearing turns into anode, and the semi-bright nickel of bottom turns into negative electrode, bright nickel layer into
It is corroded to sacrifice coating, delays corrosive medium to the corrosion rate of iron-based body, significantly improves the decay resistance of coating.
Embodiment two
Reference picture 3 and Fig. 4.A kind of battery steel shell 1 of corrosion resistance improvement, including a box hat base material 2, a bright nickel plating
The half bright oxidizing potential of nickel coating 4 and one that 3, one oxidizing potential of layer is more than the bright nickel plating layer 3 is less than the bright plating
The high-sulfur nickel coating 5 of nickel dam 3, the half bright nickel coating 4 are covered in the surface of the box hat base material 2, half bright nickel plating
The upper surface of layer 4 is covered with the high-sulfur nickel coating 5, and the upper surface of the high-sulfur nickel coating 5 is covered with the bright nickel plating layer
3。
Reference picture 3 and Fig. 4.As the preferred scheme of the present embodiment, the half bright nickel coating 4, high-sulfur nickel coating 5 and
The thickness summation of bright nickel plating layer 3 is 1.8 μm~2.3 μm.As the scheme that is more highly preferred to of the present embodiment, the high-sulfur nickel plating
The thickness of layer 5 is 0.8 μm~1.2 μm.As the preferred plan of the present embodiment, the thickness of the high-sulfur nickel coating 5 is 1 μm.
Referring to Figures 1 and 2.The thickness of the wherein described bright nickel coating 4 of semi-gloss can be 0.4 μm, while bright nickel plating layer 3
Thickness can be 0.6 μm.The thickness of the high-sulfur nickel coating 5 can be 1 μm.
Reference picture 3 and Fig. 4.The preparation method of above-mentioned battery steel shell 1 is：
A kind of 1 three layers of nickel plating technology of battery steel shell, comprise the following steps：
A, battery steel shell 1 is pre-processed.This step can be preferably：The pretreatment of battery steel shell 1 includes sequentially carrying out
Degreasing → washing → pickling → acid after wash this four procedure.
B, the pretreated surface of battery steel shell 1 is once electroplated, plating is covered with half light nickel coating.This step can
To be preferably：The once plating includes battery steel shell 1 being placed in a semi-bright nickel technique electroplate liquid electroplating 100 minutes, its
Middle semi-bright nickel technique electroplate liquid includes：300 g/l of nickel sulfate, 50 g/l of nickel chloride, 40 g/l of boric acid, cumarin 0.15
G/l, 0.15 g/l of formaldehyde, the pH of the semi-bright nickel technique electroplate liquid is 4.0, and solution temperature is 50 DEG C.
C, second time electroplating is carried out to the battery steel shell 1 after step b processing, plating is covered with a high-sulfur nickel coating.This step
Can be preferably：The second time electroplating includes that high-sulfur nickel technique electricity will be placed in including the battery steel shell 1 after step b processing
Electroplated 20 minutes in plating solution, wherein high-sulfur nickel technique electroplate liquid includes：300 g/l of nickel sulfate, 50 g/l of nickel chloride, boric acid 40
G/l, 1 g/l of benzene sulfinic acid sodium salt, 0.5 g/l of butynediols, 1 g/l of saccharin, the pH of the high-sulfur nickel technique electroplate liquid is
2.5, solution temperature is 50 DEG C.
D, the battery steel shell 1 after step c processing is electroplated three times, plating is covered with a bright nickel plating layer 3.This step
Can be preferably：The battery steel shell 1 that the plating three times is included after step c processing is placed in a bright nickel technique electroplate liquid
Plating 60 minutes, wherein bright nickel technique electroplate liquid includes：300 g/l of nickel sulfate, 50 g/l of nickel chloride, 40 g/l of boric acid,
The ml l of additive 10, the pH of the bright nickel technique electroplate liquid is 4.0, and solution temperature is 50 DEG C.
E, battery steel shell 1 is sequentially carried out reclaiming → wash → antirust treatment → and dries this four procedure.
In the present embodiment, by setting 3 and half bright nickel coating 4 of bright nickel plating layer, and in the light plating of double layer nickel
Between 3 and half bright nickel coating 4 of nickel dam, the high-sulfur that strike plating last layer thickness is about 1 μm or so plates nickel coating, due to three layers of nickel
Between potential difference be present, the half bright current potential of nickel coating 4 is more than the current potential of bright nickel plating layer 3, and the current potential of bright nickel plating layer 3 plates more than high-sulfur
The current potential of nickel dam 5, thus in corrosion process, the more negative coating of current potential is preferentially corroded, so in three layers of nickel system as anode
The anti-corrosion capability of half bright nickel coating 4 can arrive great lifting, be advantageous to further delay corrosive medium to iron-based body
Corrosion rate, and significantly improve the decay resistance of coating.
Embodiment three
Choose the Corrosion Protection analysis that three groups of samples carry out experiment product
The thickness of coating of each sample（Middle part thickness μm outside box hat）
| 1 | 2 | 3 | 4 | 5 | |
| Sample A | 2.03 | 1.98 | 1.94 | 2.13 | 1.89 |
| Sample B | 1.98 | 2.00 | 1.88 | 1.99 | 2.09 |
| Sample C | 2.12 | 1.95 | 2.22 | 1.97 | 1.90 |
Wherein sample A is using battery steel shell 1 made from existing electroplating technology, and sample B is battery described in embodiment one
Box hat 1, sample C are battery steel shell 1 described in embodiment two.
Fig. 5 shows the rust-proof effect instance graph of the progress of battery steel shell 1 salt mist experiment in the prior art.Fig. 6 shows the present invention
Battery steel shell 1 described in embodiment one carries out the rust-proof effect instance graph of salt mist experiment.Fig. 7 shows institute in the embodiment of the present invention two
State the rust-proof effect instance graph that battery steel shell 1 carries out salt mist experiment.
The condition of above salt mist experiment is：Using 5%Nacl solution spraying continuous to sample 8 hours.
Reference picture 5, Fig. 6 and Fig. 7.Sample A is existing common individual layer nickel technique, rust area 10%, protects 3 grades.Sample B
Double layer nickel technique, rust area are less than 0.25%, protect 8 grades.Tri- layers of nickel techniques of sample C, zero defect, protect 10 grades.By above-mentioned
Understand, battery steel shell 1 made from the duplex nickel plating technique disclosed using embodiment one is obtained relative to existing common individual layer nickel technique
The battery steel shell 1 obtained, its corrosion resistance lifting several times.
And battery steel shell 1 made from three layers of nickel plating technology of the disclosure of embodiment two is used, because it is the half of double layer nickel
Between bright and bright nickel, high-sulfur nickel that strike plating a layer thickness is about 1um or so, depend between three layers of nickel and current potential be present
Difference, semi-bright nickel current potential are more than bright nickel current potential, and bright nickel current potential is more than high-sulfur nickel current potential, thus in corrosion process, current potential compared with
Negative coating is preferentially corroded, so the anti-corrosion capability of the semi-bright nickel in three layers of nickel system, than in bilayer as anode
It is higher in nickel, thus the corrosion resistance of battery steel shell 1 described in embodiment two is relative to battery steel shell 1 described in embodiment one
Several times are lifted again.
Example IV
Choose the Corrosion Protection analysis that three groups of samples carry out experiment product
The thickness of coating of each sample（Middle part thickness μm outside box hat）
| 1 | 2 | 3 | 4 | 5 | |
| Sample A | 2.03 | 1.98 | 1.94 | 2.13 | 1.89 |
| Sample B | 1.98 | 2.00 | 1.88 | 1.99 | 2.09 |
| Sample C | 2.12 | 1.95 | 2.22 | 1.97 | 1.90 |
Wherein sample A is using battery steel shell 1 made from existing electroplating technology, and sample B is battery described in embodiment one
Box hat 1, sample C are battery steel shell 1 described in embodiment two.
Fig. 8 shows the rust-proof effect instance graph of the progress of battery steel shell 1 Bluepoint experiment in the prior art.Fig. 9 shows the present invention
Battery steel shell 1 described in embodiment one carries out the rust-proof effect instance graph of Bluepoint experiment.Figure 10 is shown in the embodiment of the present invention two
The battery steel shell 1 carries out the rust-proof effect instance graph of Bluepoint experiment.
The above Bluepoint experiment condition be：Sample is carried out after filter paper is soaked 5 minutes with the potassium ferricyanide+sodium chloride solution
Covering.
Reference picture 8, Fig. 9 and Figure 10.Sample A is existing common individual layer nickel technique, and it has serious Bluepoint, and area is very
Greatly.Sample B uses double layer nickel technique, slight Bluepoint.Sample C uses three layers of nickel technique, no Bluepoint.
In summary, battery steel shell 1 is relative to existing common made from the duplex nickel plating technique disclosed using embodiment one
The battery steel shell 1 that individual layer nickel technique obtains, its corrosion resistance lifting several times, and the three layers of nickel plating technology disclosed in embodiment two
Obtained battery steel shell 1 lifts several times again relative to the battery steel shell 1 in embodiment one, its corrosion resistance.
Additive used is to be used to improve battery steel shell coating surface state in field of electroplating, improve in description above
The electroplating additive of its electrical property and welding performance, such additives are the common technology in the field, thus herein not to it
Specific composition is described in detail.
The embodiment of the present invention is above are only, but the design concept of the present invention is not limited thereto, it is all to utilize this
Conceive the change that unsubstantiality is carried out to the present invention, the behavior for invading the scope of the present invention all should be belonged to.
Claims (2)
1. a kind of three layers of nickel plating technology of battery steel shell, it is characterised in that comprise the following steps：A, battery steel shell is located in advance
Reason；B, pretreated battery steel shell surface is once electroplated, plating is covered with half light nickel coating；C, to passing through step b
Battery steel shell after processing carries out second time electroplating, and plating is covered with a high-sulfur nickel coating；D, to the battery steel shell after step c processing
Electroplated three times, plating is covered with a bright nickel plating layer；The oxidizing potential of the bright nickel plating layer is less than described half bright nickel coating, institute
The oxidizing potential for stating high-sulfur nickel coating is less than the bright nickel plating layer, and in stepb, the once plating is included battery steel shell
It is placed in a semi-bright nickel technique electroplate liquid and electroplates 100 minutes, wherein semi-bright nickel technique electroplate liquid includes：300 grams of nickel sulfate/
Liter, 50 g/l of nickel chloride, 40 g/l of boric acid .15 g/l of cumarin 0 .15 g/l of formaldehyde 0, semi-bright nickel technique electricity
The pH of plating solution is 4 .0, and solution temperature is 50 DEG C, and in step c, the second time electroplating includes to include after step b processing
Battery steel shell be placed in a high-sulfur nickel technique electroplate liquid and electroplate 20 minutes, wherein high-sulfur nickel technique electroplate liquid includes：Nickel sulfate
300 g/l, 50 g/l of nickel chloride, 40 g/l of boric acid, 1 g/l of benzene sulfinic acid sodium salt .5 g/l of butynediols 0, saccharin 1
G/l, the pH of the high-sulfur nickel technique electroplate liquid is 2 .5, and solution temperature is 50 DEG C, and in step d, the plating three times includes
Battery steel shell after step c processing, which is placed in a bright nickel technique electroplate liquid, electroplates 60 minutes, wherein bright nickel technique electricity
Plating solution includes：300 g/l of nickel sulfate, 50 g/l of nickel chloride, 40 g/l of boric acid, the ml l of additive 10, the bright nickel work
The pH of skill electroplate liquid is 4 .0, and solution temperature is 50 DEG C.
A kind of 2. three layers of nickel plating technology of battery steel shell as claimed in claim 1, it is characterised in that：Also it is located at the step including one
Step e after rapid d, battery steel shell recovery that the step e includes sequentially carrying out, washing, antirust treatment, dry this four work
Sequence, in step a, this four work is washed after battery steel shell degreasing, washing, pickling and acid that pretreatment includes sequentially carrying out
Sequence.
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| CN201510965899.5A CN105525317B (en) | 2015-12-22 | 2015-12-22 | Battery steel shell made from a kind of three layers of nickel plating technology of battery steel shell and the technique |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510965899.5A CN105525317B (en) | 2015-12-22 | 2015-12-22 | Battery steel shell made from a kind of three layers of nickel plating technology of battery steel shell and the technique |
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| CN109301094B (en) * | 2017-07-25 | 2024-05-31 | 宁波堇山新材料有限公司 | Ni-plated steel strip, battery steel shell using same and preparation method of steel shell |
| CN112680633A (en) * | 2020-12-07 | 2021-04-20 | 迈瑞沙(宁波)新材料科技有限公司 | Nickel-cobalt-sulfur composite material and preparation method and application thereof |
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| CN104818508B (en) * | 2015-03-31 | 2017-05-03 | 江苏九天光电科技有限公司 | Precision nickel composite steel strip preparation method |
| CN205406570U (en) * | 2015-12-22 | 2016-07-27 | 福建金杨科技股份有限公司 | Battery steel casing of anti -corrosion performance improvement |
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