CN107069042A - A kind of lead-acid accumulator light-type grid and preparation method thereof - Google Patents
A kind of lead-acid accumulator light-type grid and preparation method thereof Download PDFInfo
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- CN107069042A CN107069042A CN201710339644.7A CN201710339644A CN107069042A CN 107069042 A CN107069042 A CN 107069042A CN 201710339644 A CN201710339644 A CN 201710339644A CN 107069042 A CN107069042 A CN 107069042A
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- Prior art keywords
- lead
- plating
- grid
- acid
- aluminium alloy
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- 239000002253 acid Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000007747 plating Methods 0.000 claims abstract description 108
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000011133 lead Substances 0.000 claims abstract description 53
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 41
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 23
- 238000009713 electroplating Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 108010010803 Gelatin Proteins 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229920000159 gelatin Polymers 0.000 claims description 10
- 239000008273 gelatin Substances 0.000 claims description 10
- 235000019322 gelatine Nutrition 0.000 claims description 10
- 235000011852 gelatine desserts Nutrition 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 10
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 229910000648 terne Inorganic materials 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 6
- 229940038773 trisodium citrate Drugs 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- 239000007832 Na2SO4 Substances 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 229940046892 lead acetate Drugs 0.000 claims description 5
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- -1 brightener 1ml/L Substances 0.000 claims description 2
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical class OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 238000007772 electroless plating Methods 0.000 claims description 2
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 12
- 239000004411 aluminium Substances 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 6
- 239000011241 protective layer Substances 0.000 abstract description 3
- 239000011149 active material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001128 Sn alloy Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001245 Sb alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002140 antimony alloy Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DBRHOLYIDDOQSD-UHFFFAOYSA-N alumane;lead Chemical compound [AlH3].[Pb] DBRHOLYIDDOQSD-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- 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
- C25D3/34—Electroplating: Baths therefor from solutions of lead
- C25D3/36—Electroplating: Baths therefor from solutions of lead characterised by the organic bath constituents used
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
-
- 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
Abstract
A kind of lead-acid accumulator light-type grid and preparation method thereof, including aluminium alloy grid (1), using plating or chemical plating method be plated in the nickel coating (2) of aluminium alloy grid surface, the plating lead layer (3) of nickel plating layer surface is plated in using electro-plating method.Compared with traditional metal grid, the addition of substrate aluminium can greatly improve grid performance in the present invention, and can reduce the consumption of lead, thus mitigate the weight of battery.Nickel coating is firmly combined with aluminium alloy plate grid base bottom, is formed the protective layer of structural integrity, can be greatly improved the specific energy and discharge capacity of battery.The light-type grid preparation section of the present invention is simple, and preparation cost is low, durable in use, can be used as the pole plate of Large Copacity, high-power output and long circulation life.
Description
Technical field
The present invention relates to Lead-acid Battery Technology field, and in particular to lead-acid accumulator grid.
Technical background
Effect of the grid in battery has three aspects：One is to play skeletal support and viscous as the carrier of active material
The effect of attached active material；Two be to play a part of afflux as the conductor of electric current, conflux and defeated stream；Three be as pole plate
Equal fluid plays a part of making balanced current distribution into active material.
The alloy of the making grid used at present in production has three classes：One class is traditional lead-antimony alloy, and the content of antimony exists
4%~7% mass fraction；One class is low antimony or superlow antimony alloy, and the content of antimony is in 2% mass fraction or less than 1% mass
Fraction；One class is lead calcium series, and actual is lead-calcium-tin-aluminium quaternary alloy, and the content of calcium is in 0.06%~0.1% mass point
Number.The anode plate grid that above-mentioned alloy is cast, can all be oxidized to lead sulfate and brown lead oxide, finally in battery charging process
Cause to lose the effect of support active material and make battery failure；Or due to the formation of brown lead oxide corrosion layer, make metal
Stress is produced, makes the long large deformation of grid, this pole plate to be made integrally to be destroyed when deforming more than 4%, active material and grid
Loose contact and come off, or at bus-bar it is short-circuit.
Lead-acid accumulator undergoes the development of more than 100 years, although its technology achieves very big breakthrough in all fields, but also
There are many deficiencies, volume is big, weight is heavy, active material utilization is low, specific energy low (30-40Wh/kg) is that it is most prominent
The deficiency and shortcoming gone out.From the point of view of the composition structure of lead-acid accumulator, the positive and negative grid of traditional lead acid batteries is main by density
Larger metal is constituted, add the lead in the weight of lead-acid battery itself, grid quite a few only act as support and
The effect confluxed, and it is not involved in the effect of battery itself discharge and recharge, therefore the specific energy of influence lead-acid battery.
Aluminium and its alloy are cheap, and density is low, but intensity is high, and plasticity is good, can be processed into various section bars, possess good
Electric conductivity, thermal conductivity and corrosion resistance, the properties of battery can be effectively lifted as lead-acid battery grid material.But metal
Aluminium is the metal of a kind of very living group, and the alundum (Al2O3) that surface is formed is a kind of amphoteric oxide, in sulfuric acid solution intolerant to
Corruption candle.Therefore, metallic aluminium as the key of grid matrix be can its surface cover one layer with substrate be firmly combined with, structure
Complete protective layer blocks the corrosion of electrolyte.
In recent years, it is many with the research of aluminium base light-type grid for lead-acid accumulator, such as Chinese patent
201310730624.4 prepare aluminium alloy grid and after its electroplate using gravity casting method, the side prepared with terne metal
Frame carries out embedded cooperation and is used as grid material.Chinese patent 201010524211.7 with titanium or titanium alloy or copper or copper alloy or
Aluminum or aluminum alloy powder or sheet material are substrate, and the powder that substrate is added into two or more predetermined substance is obtained through roll forming
Obtain light plate grid for lead-acid storage battery.Chinese patent 201120070374.2, which is used, the countless cellular holes with carbon fibre material
Cave aluminium foil honeycomb grid, lead plaster is filled up in hole, is used as polar plate of lead acid storage battery.Chinese patent 201310467238.0 is used
Grid is made in carbon, aluminium or electrical conductivity alloy, and lead or metal are sprayed on after grid surface into strongly extruding or directly strong with rolled lead
Power extrusion cladding prepares light-type grid in grid surface.Chinese patent 201110310109.1 is using porous aluminum or aluminum alloy
Matrix, after pretreatment using fused salt chemistry lead plating and metal bath PROCESS FOR TREATMENT, obtains lead-acid battery with high specific surface area porous
Aluminium base light plate grid etc..But these patented technologies all exist in terms of operation ease, preparation cost and aluminium lead binding ability
It is not enough.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of plating lead layer adhesion in aluminum alloy substrate
By force, lead-acid accumulator light-type grid that grid is lightweight, specific energy is higher and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：
A kind of lead-acid accumulator light-type grid and preparation method thereof, including aluminium alloy grid, using plating or chemical plating
Method is plated in the nickel coating of aluminium alloy grid surface, the plating lead layer of nickel plating layer surface is plated in using electro-plating method.
Aluminium alloy grid of the present invention is netted grid or radial grid or grid-like grid.It is described to use plating side
The technical parameter that nickel coating is plated in aluminium alloy grid surface is by method：Electronickelling liquid composition is NiSO4·6H250~70g/L of O,
80~110g/L of trisodium citrate, H3BO35~8g/L, 8~10g/L of NaCl, Na2SO435~45g/L, 0.3~0.5g/ of gelatin
L, using aluminium alloy grid as negative electrode, the close nickel plate of unilateral area be anode, 30~45 DEG C of plating temperature, current density 1~
3Adm-2, electroplating time 30min~50min.Nickel coating is plated in the technology of aluminium alloy grid surface by the use chemical plating method
Parameter is：Chemical nickel-plating liquid composition is NiSO4·6H2O20~50g/L, 20~35g/L of sodium hypophosphite, 15~30ml/ of lactic acid
L, 1~3g/L of succinic acid, 1~3g/L of trisodium citrate, brightener 1ml/L, stabilizer 0.5g/L, add ammoniacal liquor regulation pH value and arrive
4.4~4.6,85 DEG C~90 DEG C of plating temperature, electroless plating time 1h~2h.The brightener composition is 1,4- butynediols 450
~510g/L, 130~160g/L of epoxychloropropane, 3~5g/L of para toluene sulfonamide, 30~40g/L of sodium hydroxide；Stabilizer is
Sodium Thiosulfate or thiocarbamide or lead chloride.The terne metal that the lead plating composition of layer is pure lead or Theil indices are 0~5%；Lead plating
Layer is obtained using pyrovinic acid system or fluoboric acid system electro-plating method；The pyrovinic acid system electroplating technology parameter is：Electricity
Lead plating liquid composition is 80~120ml/L of pyrovinic acid, 150~200g/L of pyrovinic acid lead, 0~50g/L Sn2+, sodium potassium tartrate tetrahydrate
2~5g/L, 0.5~5g/L of additive, pH=1~1.5,40 DEG C of plating temperature, current density 3Adm-2, 3~7h of electroplating time；
The fluoboric acid system electroplating technology parameter is：Lead plating liquid composition be 190~220ml/L of fluoboric acid, 15~20g/L of boric acid,
180~220g/L of lead acetate, 0~30g/L of stannous fluoboric acid, gelatin 1g/L, thiocarbamide 0.2g/L, 40 DEG C of plating temperature, electric current is close
Spend 3Adm-2, 4~7h of electroplating time.The additive is polyethylene glycol or hydroquinones.The thickness of the aluminium alloy grid is
1mm~2mm, nickel plating layer thick is 10 μm~50 μm, and lead plating thickness degree is 0.1mm~0.5mm.
The aluminium base light-type grid material of the present invention can be used for making accumulator plus-minus polar plate, with traditional metal grid phase
Than the addition of substrate aluminium can greatly improve grid performance in the present invention, and can reduce the consumption of lead, thus mitigate battery
Weight.Nickel coating is firmly combined with aluminium alloy plate grid base bottom, is formed the protective layer of structural integrity, can be greatly improved the matter of battery
Measure specific energy and discharge capacity.The light-type grid preparation section of the present invention is simple, and preparation cost is low, durable in use, can be used as big
The pole plate of capacity, high-power output and long circulation life.
Brief description of the drawings
Fig. 1 is the profile of lead-acid accumulator light-type grid of the present invention.
Embodiment
As shown in figure 1, the lead-acid accumulator of present invention light-type grid includes aluminium alloy grid 1, using plating or chemistry
Electroplating method is plated in the nickel coating 2 of aluminium alloy grid surface, the plating lead layer 3 of nickel plating layer surface is plated in using electro-plating method.
Embodiment one：Reticulated aluminum alloy grid is placed in electronickelling liquid and electroplated, electronickelling liquid composition is NiSO4·
6H2O70g/L, trisodium citrate 90g/L, H3BO35g/L、NaCl 10g/L、Na2SO440g/L, gelatin 0.45g/L, with aluminium alloy
Grid is negative electrode, and the close nickel plate of unilateral area is anode, 40 DEG C of plating temperature, current density 2Adm-2, electroplating time 30min,
Nickel plating cleans drying after finishing with clear water, the grid after nickel plating is placed in into pyrovinic acid system lead plating again, lead plating liquid composition is
Pyrovinic acid 120ml/L, pyrovinic acid lead 200g/L, sodium potassium tartrate tetrahydrate 2g/L, polyethylene glycol 0.5g/L, pH=1~1.2 are applied
40 DEG C of temperature is plated, by current density 3Adm-27h is electroplated, the lead-acid accumulator light-type grid that surface is pure lead-coat is obtained.Aluminium
The thickness of alloy grid is 1mm, and nickel plating layer thick is 10 μm, and pure lead-coat thickness is 0.1mm.
Embodiment two：Radial aluminium alloy grid is placed in electronickelling liquid and electroplates 50min, electronickelling liquid composition is
NiSO4·6H2O60g/L, trisodium citrate 110g/L, H3BO37g/L、NaCl 8g/L、Na2SO445g/L, gelatin 0.5g/L, with
Aluminium alloy grid is negative electrode, and the close nickel plate of unilateral area is anode, 45 DEG C of plating temperature, current density 1Adm-2, electroplating time
40min, nickel plating cleans drying after finishing with clear water.Grid after nickel plating is placed in the plating lead plating of pyrovinic acid system, plating again
Lead liquid composition is pyrovinic acid 90ml/L, pyrovinic acid lead 150g/L, 20g/L Sn2+, sodium potassium tartrate tetrahydrate 4g/L, hydroquinones
1.5g/L, pH=1~1.5,40 DEG C of plating temperature, by current density 3Adm-25h is electroplated, it is stanniferous to obtain surface plating lead layer
The lead-acid accumulator light-type grid of 1.73% terne metal.The thickness of aluminium alloy grid is 2mm, and nickel plating layer thick is 30 μ
M, pb-sn alloy plating thickness is 0.3mm.
Embodiment three：Grid-like aluminium alloy grid is placed in electronickelling liquid and electroplates 40min, electronickelling liquid composition is
NiSO4·6H2O50g/L, trisodium citrate 80g/L, H3BO38g/L、NaCl 9g/L、Na2SO435g/L, gelatin 0.3g/L, with
Aluminium alloy grid is negative electrode, and the close nickel plate of unilateral area is anode, 30 DEG C of plating temperature, current density 3Adm-2, electroplating time
50min, nickel plating cleans drying after finishing with clear water..Grid after nickel plating is placed in the plating lead plating of pyrovinic acid system, plating again
Lead liquid composition is pyrovinic acid 80ml/L, pyrovinic acid lead 180g/L, 50g/L Sn2+, sodium potassium tartrate tetrahydrate 5g/L, polyethylene glycol
5g/L, pH=1.2~1.5,40 DEG C of plating temperature, by current density 3Adm-23h is electroplated, it is stanniferous 5% to obtain surface plating lead layer
Terne metal lead-acid accumulator light-type grid.The thickness of aluminium alloy grid is 1.5mm, and nickel plating layer thick is 20 μm, lead
Tin alloy coat thickness is 0.5mm.
Example IV：Grid-like aluminium alloy grid is placed in chemical nickel-plating liquid, chemical plating 1 hour when temperature is 90 DEG C,
Chemical nickel-plating liquid composition is NiSO4·6H2O30g/L, sodium hypophosphite 30g/L, lactic acid 24ml/L, succinic acid 2g/L, citric acid
(brightener composition is Isosorbide-5-Nitrae-butynediols 480g/L, epoxychloropropane 130g/L, to toluene sulphur by trisodium 1g/L, brightener 1ml/L
Acid amides 5g/L, sodium hydroxide 40g/L), Sodium Thiosulfate 0.5g/L, add ammoniacal liquor and adjust pH value to 4.4~4.6.Chemical plating is complete
Cheng Houyong clear water is dried after cleaning.Grid after nickel plating is placed in the plating lead plating of pyrovinic acid system again, lead plating method is with implementing
Example two is identical, obtains the lead-acid accumulator light-type grid that overlay coating is terne metal.The thickness of aluminium alloy grid is
1.5mm, nickel plating layer thick is 25 μm, and pb-sn alloy plating thickness is 0.4mm.
Embodiment five：Radial aluminium alloy grid is placed in chemical nickel-plating liquid, chemical plating 2 hours when temperature is 85 DEG C,
Chemical nickel-plating liquid composition is NiSO4·6H2O50g/L, sodium hypophosphite 20g/L, lactic acid 30ml/L, succinic acid 3g/L, citric acid
(brightener composition is Isosorbide-5-Nitrae-butynediols 510g/L, epoxychloropropane 150g/L, to toluene sulphur by trisodium 3g/L, brightener 1ml/L
Acid amides 3g/L, sodium hydroxide 30g/L), thiocarbamide 0.5g/L, add ammoniacal liquor and adjust pH value to 4.4~4.6.Used after the completion of chemical plating
Clear water is dried after cleaning.Grid after nickel plating is placed in the plating lead plating of fluoboric acid system, lead plating liquid composition is fluoboric acid
220ml/L, boric acid 20g/L, lead acetate 180g/L, stannous fluoboric acid 20g/L, gelatin 1g/L, thiocarbamide 0.2g/L, plating temperature 40
DEG C, by current density 3Adm-26h is electroplated, the lead acid storage battery that overlay coating plates lead layer for the terne metal of stanniferous amount 2.07% is obtained
Pond light-type grid.The thickness of aluminium alloy grid is 2mm, and nickel plating layer thick is 40 μm, and pb-sn alloy plating thickness is 0.4mm.
Embodiment six：Grid-like aluminium alloy grid is placed in chemical nickel-plating liquid, chemical plating 1.5 is small when temperature is 88 DEG C
When, chemical nickel-plating liquid composition be the same as Example four.Grid after nickel plating is placed in the plating lead plating of fluoboric acid system, lead plating liquid composition
For fluoboric acid 190ml/L, boric acid 18g/L, lead acetate 200g/L, stannous fluoboric acid 30g/L, gelatin 1g/L, thiocarbamide 0.2g/L is applied
40 DEG C of temperature is plated, by current density 3Adm-24h is electroplated, it is the terne metal plating lead layer that stanniferous amount is 1.94% to obtain overlay coating
Lead-acid accumulator light-type grid.The thickness of aluminium alloy grid is 1.5mm, and nickel plating layer thick is 30 μm, pb-sn alloy plating
Thickness is 0.3mm.
Embodiment seven：Reticulated aluminum alloy grid is placed in chemical nickel-plating liquid, chemical plating 1.5 hours when temperature is 90 DEG C,
Chemical nickel-plating liquid composition is NiSO4·6H2O20g/L, sodium hypophosphite 35g/L, lactic acid 15ml/L, succinic acid 1g/L, citric acid
(brightener composition is Isosorbide-5-Nitrae-butynediols 450g/L, epoxychloropropane 160g/L, to toluene sulphur by trisodium 2g/L, brightener 1ml/L
Acid amides 4g/L, sodium hydroxide 35g/L), lead chloride 0.5g/L, add ammoniacal liquor and adjust pH value to 4.4~4.6.After the completion of chemical plating
Dried after being cleaned with clear water.Grid after nickel plating is placed in the plating lead plating of fluoboric acid system, lead plating liquid composition is fluoboric acid
200ml/L, boric acid 15g/L, lead acetate 220g/L, gelatin 1g/L, thiocarbamide 0.2g/L, 40 DEG C of plating temperature, by current density
3Adm-27h is electroplated, the lead-acid accumulator light-type grid that overlay coating is pure lead is obtained.The thickness of aluminium alloy grid is 1.5mm,
Nickel plating layer thick is 40 μm, and lead plating thickness degree is 0.4mm.
Claims (8)
1. a kind of lead-acid accumulator light-type grid and preparation method thereof, it is characterized in that, including aluminium alloy grid (1), using electricity
Plating or chemical plating method are plated in the nickel coating (2) of aluminium alloy grid surface, the lead plating of nickel plating layer surface are plated in using electro-plating method
Layer (3).
2. a kind of lead-acid accumulator light-type grid according to claim 1 and preparation method thereof, it is characterized in that, the aluminium
Alloy grid is netted grid or radial grid or grid-like grid.
3. a kind of lead-acid accumulator light-type grid according to claim 1 and preparation method thereof, it is characterized in that, it is described to adopt
It is by the technical parameter that nickel coating (2) is plated in aluminium alloy grid (1) surface with electro-plating method：Electronickelling liquid composition is NiSO4·
6H2O50~70g/L, 80~110g/L of trisodium citrate, H3BO35~8g/L, 8~10g/L of NaCl, Na2SO435~45g/L,
0.3~0.5g/L of gelatin, using aluminium alloy grid as negative electrode, the close nickel plate of unilateral area be anode, 30~45 DEG C of plating temperature,
1~3Adm of current density-2, electroplating time 30min~50min.
4. a kind of lead-acid accumulator light-type grid according to claim 1 and preparation method thereof, it is characterized in that, it is described to adopt
It is by the technical parameter that nickel coating (2) is plated in aluminium alloy grid (1) surface with chemical plating method：Chemical nickel-plating liquid composition is
NiSO4·6H2O20~50g/L, 20~35g/L of sodium hypophosphite, 15~30ml/L of lactic acid, 1~3g/L of succinic acid, citric acid three
1~3g/L of sodium, brightener 1ml/L, stabilizer 0.5g/L, addition ammoniacal liquor regulation pH value to 4.4~4.6,85 DEG C of plating temperature~
90 DEG C, electroless plating time 1h~2h.
5. a kind of lead-acid accumulator light-type grid according to claim 4 and preparation method thereof, it is characterized in that, the light
Bright dose of composition be 450~510g/L of 1,4- butynediols, 130~160g/L of epoxychloropropane, 3~5g/L of para toluene sulfonamide,
30~40g/L of sodium hydroxide；Stabilizer is Sodium Thiosulfate or thiocarbamide or lead chloride.
6. a kind of lead-acid accumulator light-type grid according to claim 1 and preparation method thereof, it is characterized in that, the plating
The terne metal that lead layer composition is pure lead or Theil indices are 0~5%；Lead layer is plated using pyrovinic acid system or fluoboric acid system electricity
Electroplating method is obtained；The pyrovinic acid system electroplating technology parameter is：Lead plating liquid composition be 80~120ml/L of pyrovinic acid,
150~200g/L of pyrovinic acid lead, 0~50g/L Sn2+, 2~5g/L of sodium potassium tartrate tetrahydrate, 0.5~5g/L of additive, pH=1~
1.5,40 DEG C of plating temperature, current density 3Adm-2, 3~7h of electroplating time；The fluoboric acid system electroplating technology parameter is：Electricity
Lead plating liquid composition be 190~220ml/L of fluoboric acid, 15~20g/L of boric acid, 180~220g/L of lead acetate, stannous fluoboric acid 0~
30g/L, gelatin 1g/L, thiocarbamide 0.2g/L, 40 DEG C of plating temperature, current density 3Adm-2, 4~7h of electroplating time.
7. a kind of lead-acid accumulator light-type grid according to claim 6 and preparation method thereof, it is characterized in that, it is described to add
Plus agent is polyethylene glycol or hydroquinones.
8. a kind of lead-acid accumulator light-type grid according to any one of claim 1~7 and preparation method thereof, it is special
Levying is, the thickness of the aluminium alloy grid is 1mm~2mm, and nickel plating layer thick is 10 μm~50 μm, and lead plating thickness degree is 0.1mm
~0.5mm.
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| CN109841837A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | Lead carbon battery grid and preparation and application of the galvanoplastic preparation with three-dimensional structure |
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| CN110923769A (en) * | 2019-10-21 | 2020-03-27 | 肇庆理士电源技术有限公司 | Electroplating method of thin lead coating of carbon grid of lead-carbon battery |
| CN110923769B (en) * | 2019-10-21 | 2021-04-20 | 肇庆理士电源技术有限公司 | Electroplating method of thin lead coating of carbon grid of lead-carbon battery |
| CN112736366A (en) * | 2020-12-29 | 2021-04-30 | 上海应用技术大学 | Method for cast welding light metal negative grid lead storage battery busbar |
| CN116454524A (en) * | 2023-05-31 | 2023-07-18 | 三一红象电池有限公司 | Explosion-proof valve and preparation method and application thereof |
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