CN107069042A - 一种铅酸蓄电池用轻型板栅及其制备方法 - Google Patents
一种铅酸蓄电池用轻型板栅及其制备方法 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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- 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
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- 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
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- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- H01M4/685—Lead alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
一种铅酸蓄电池用轻型板栅及其制备方法，包括铝合金板栅(1)、采用电镀或化学镀方法镀在铝合金板栅表面的镀镍层(2)、采用电镀方法镀在镀镍层表面的镀铅层(3)。与传统的铅合金板栅相比，本发明中基底铝的加入可大幅提高板栅性能，并且可减少铅的用量，由此减轻蓄电池的重量。镀镍层与铝合金板栅基底结合牢固，形成结构完整的保护层，可大幅提高蓄电池的质量比能量及放电容量。本发明的轻型板栅制备工序简单，制备成本低，经久耐用，可用作大容量、高功率输出和长循环寿命的极板。
Description
技术领域
本发明涉及铅酸蓄电池技术领域，具体涉及铅酸蓄电池极板板栅。
技术背景
板栅在蓄电池中的作用有三个方面：一是作为活性物质的载体起着骨架支撑和粘附活性物质的作用；二是作为电流的传导体起着集流、汇流和输流的作用；三是作为极板的均流体起着使电流均匀分布到活性物质中的作用。
目前生产上使用的制作板栅的合金有三类：一类是传统的铅锑合金，锑的含量在4％～7％质量分数；一类是低锑或超低锑合金，锑的含量在2％质量分数或者低于1％质量分数；一类是铅钙系列，实际为铅-钙-锡-铝四元合金，钙的含量在0.06％～0.1％质量分数。上述合金铸成的正极板栅，在蓄电池充电过程中都会被氧化成硫酸铅和二氧化铅，最后导致丧失支撑活性物质的作用而使电池失效；或者由于二氧化铅腐蚀层的形成，使铅合金产生应力，使板栅长大变形，这种变形超过4％时将使极板整体遭到破坏，活性物质与板栅接触不良而脱落，或在汇流排处短路。
铅酸蓄电池经历一百多年的发展，虽然其技术在各个方面取得了很大突破，但还存在许多不足，体积大、重量重、活性物质利用率低、质量比能量低(30-40Wh/kg)是其最突出的不足和缺点。从铅酸蓄电池的组成结构来看，传统铅酸蓄电池的正负板栅主要由密度较大的铅合金构成，增加了铅酸电池自身的重量，板栅中的铅相当一部分只是充当支撑和汇流的作用，并不参与电池自身充放电的作用，因此影响铅酸电池的比能量。
铝及其合金价格便宜，密度低，但强度高，塑性好，可加工成各种型材，具备良好的导电性、导热性和耐蚀性，作为铅酸电池板栅材料能够有效提升电池的各项性能。但是金属铝是一种十分活拨的金属，表面形成的三氧化二铝是一种两性氧化物，在硫酸溶液中不耐腐烛。因此，金属铝作为板栅基体的关键在于能否在其表面覆盖一层与基底结合牢固、结构完整的保护层来阻断电解液的腐蚀。
近年来，针对铅酸蓄电池用铝基轻型板栅的研究很多，如中国专利201310730624.4采用重力浇铸法制备铝合金栅格并在其表面镀银后，与铅锡合金制备的边框进行嵌入式配合作为板栅材料。中国专利201010524211.7以钛或钛合金或铜或铜合金或铝或铝合金粉末或板材为基底，将基底添加二种或二种以上特定物质的粉末经轧制成型获得铅酸蓄电池轻质板栅。中国专利201120070374.2使用有无数附有碳纤维材料的蜂巢式孔穴铝箔蜂巢板栅，在孔穴内填满铅膏，用做铅酸蓄电池极板。中国专利201310467238.0用碳、铝或导电合金制成板栅，将铅或铅合金喷涂在板栅表面后强力挤压或直接用薄铅板强力挤压包覆在板栅表面，制备轻型板栅。中国专利201110310109.1使用多孔铝或铝合金为基体，经预处理后采用熔盐化学镀铅及金属浴工艺处理，获得铅酸电池用高比表面积多孔铝基轻质板栅等。但这些专利技术在操作便利性、制备成本及铝铅结合性能等方面都存在不足。
发明内容
为了克服上述现有技术的不足，本发明提供一种镀铅层在铝合金基底上结合力强、板栅重量轻、比能量较高的铅酸蓄电池用轻型板栅及其制备方法。
本发明的目的通过如下技术方案实现：
一种铅酸蓄电池用轻型板栅及其制备方法，包括铝合金板栅、采用电镀或化学镀方法镀在铝合金板栅表面的镀镍层、采用电镀方法镀在镀镍层表面的镀铅层。
本发明所述铝合金板栅为网状板栅或辐射状板栅或方格状板栅。所述采用电镀方法将镀镍层镀在铝合金板栅表面的技术参数为：电镀镍液成分为NiSO4·6H2O 50～70g/L、柠檬酸三钠80～110g/L、H3BO35～8g/L、NaCl 8～10g/L、Na2SO435～45g/L、明胶0.3～0.5g/L，以铝合金板栅为阴极，单侧面积接近的镍板为阳极，施镀温度30～45℃，电流密度1～3Adm-2，电镀时间30min～50min。所述采用化学镀方法将镀镍层镀在铝合金板栅表面的技术参数为：化学镀镍液成分为NiSO4·6H2O20～50g/L、次亚磷酸钠20～35g/L、乳酸15～30ml/L、丁二酸1～3g/L、柠檬酸三钠1～3g/L、光亮剂1ml/L、稳定剂0.5g/L，加入氨水调节pH值到4.4～4.6，施镀温度85℃～90℃，化学镀时间1h～2h。所述光亮剂成分为1,4-丁炔二醇450～510g/L、环氧氯丙烷130～160g/L、对甲苯磺酰胺3～5g/L、氢氧化钠30～40g/L；稳定剂为次亚硫酸钠或硫脲或氯化铅。所述镀铅层成分为纯铅或锡含量为0～5％的铅锡合金；镀铅层采用甲基磺酸体系或氟硼酸体系电镀方法获得；所述甲基磺酸体系电镀技术参数为：电镀铅液成分为甲基磺酸80～120ml/L、甲基磺酸铅150～200g/L、0～50g/L Sn2+、酒石酸钾钠2～5g/L、添加剂0.5～5g/L、pH＝1～1.5，施镀温度40℃，电流密度3Adm-2，电镀时间3～7h；所述氟硼酸体系电镀技术参数为：电镀铅液成分为氟硼酸190～220ml/L、硼酸15～20g/L、醋酸铅180～220g/L、氟硼酸亚锡0～30g/L、明胶1g/L、硫脲0.2g/L，施镀温度40℃，电流密度3Adm-2，电镀时间4～7h。所述添加剂为聚乙二醇或对苯二酚。所述铝合金板栅的厚度为1mm～2mm，镀镍层厚度为10μm～50μm，镀铅层厚度为0.1mm～0.5mm。
本发明的铝基轻型板栅材料可用于制作蓄电池正负极板，与传统的铅合金板栅相比，本发明中基底铝的加入可大幅提高板栅性能，并且可减少铅的用量，由此减轻蓄电池的重量。镀镍层与铝合金板栅基底结合牢固，形成结构完整的保护层，可大幅提高蓄电池的质量比能量及放电容量。本发明的轻型板栅制备工序简单，制备成本低，经久耐用，可用作大容量、高功率输出和长循环寿命的极板。
附图说明
图1是本发明铅酸蓄电池用轻型板栅的剖面图。
具体实施方式
如图1所示，本发明的铅酸蓄电池用轻型板栅包括铝合金板栅1、采用电镀或化学镀方法镀在铝合金板栅表面的镀镍层2、采用电镀方法镀在镀镍层表面的镀铅层3。
实施例一：将网状铝合金板栅置于电镀镍液中进行电镀，电镀镍液成分为NiSO4·6H2O70g/L、柠檬酸三钠90g/L、H3BO35g/L、NaCl 10g/L、Na2SO440g/L、明胶0.45g/L，以铝合金板栅为阴极，单侧面积接近的镍板为阳极，施镀温度40℃，电流密度2Adm-2，电镀时间30min，镀镍完毕后用清水洗净烘干，将镀镍后的板栅再置于甲基磺酸体系镀铅，电镀铅液成分为甲基磺酸120ml/L、甲基磺酸铅200g/L、酒石酸钾钠2g/L、聚乙二醇0.5g/L，pH＝1～1.2，施镀温度40℃，按电流密度3Adm-2电镀7h，获得表面为纯铅镀层的铅酸蓄电池用轻型板栅。铝合金板栅的厚度为1mm，镀镍层厚度为10μm，纯铅镀层厚度为0.1mm。
实施例二：将辐射状铝合金板栅置于电镀镍液中电镀50min，电镀镍液成分为NiSO4·6H2O60g/L、柠檬酸三钠110g/L、H3BO37g/L、NaCl 8g/L、Na2SO445g/L、明胶0.5g/L，以铝合金板栅为阴极，单侧面积接近的镍板为阳极，施镀温度45℃，电流密度1Adm-2，电镀时间40min，镀镍完毕后用清水洗净烘干。将镀镍后的板栅再置于甲基磺酸体系电镀镀铅，电镀铅液成分为甲基磺酸90ml/L、甲基磺酸铅150g/L、20g/L Sn2+、酒石酸钾钠4g/L，对苯二酚1.5g/L，pH＝1～1.5，施镀温度40℃，按电流密度3Adm-2电镀5h，获得表面镀铅层为含锡1.73％的铅锡合金的铅酸蓄电池用轻型板栅。铝合金板栅的厚度为2mm，镀镍层厚度为30μm，铅锡合金镀层厚度为0.3mm。
实施例三：将方格状铝合金板栅置于电镀镍液中电镀40min，电镀镍液成分为NiSO4·6H2O50g/L、柠檬酸三钠80g/L、H3BO38g/L、NaCl 9g/L、Na2SO435g/L、明胶0.3g/L，以铝合金板栅为阴极，单侧面积接近的镍板为阳极，施镀温度30℃，电流密度3Adm-2，电镀时间50min，镀镍完毕后用清水洗净烘干。。将镀镍后的板栅再置于甲基磺酸体系电镀镀铅，电镀铅液成分为甲基磺酸80ml/L、甲基磺酸铅180g/L、50g/L Sn2+、酒石酸钾钠5g/L，聚乙二醇5g/L，pH＝1.2～1.5，施镀温度40℃，按电流密度3Adm-2电镀3h，获得表面镀铅层为含锡5％的铅锡合金的铅酸蓄电池用轻型板栅。铝合金板栅的厚度为1.5mm，镀镍层厚度为20μm，铅锡合金镀层厚度为0.5mm。
实施例四：将方格状铝合金板栅置于化学镀镍液中，温度为90℃时化学镀1小时，化学镀镍液成分为NiSO4·6H2O30g/L、次亚磷酸钠30g/L、乳酸24ml/L、丁二酸2g/L、柠檬酸三钠1g/L、光亮剂1ml/L(光亮剂成分为1,4-丁炔二醇480g/L，环氧氯丙烷130g/L，对甲苯磺酰胺5g/L，氢氧化钠40g/L)、次亚硫酸钠0.5g/L，加入氨水调节pH值到4.4～4.6。化学镀完成后用清水洗净后烘干。将镀镍后的板栅再置于甲基磺酸体系电镀镀铅，镀铅方法与实施例二相同，获得表面镀层为铅锡合金的铅酸蓄电池用轻型板栅。铝合金板栅的厚度为1.5mm，镀镍层厚度为25μm，铅锡合金镀层厚度为0.4mm。
实施例五：将辐射状铝合金板栅置于化学镀镍液中，温度为85℃时化学镀2小时，化学镀镍液成分为NiSO4·6H2O50g/L、次亚磷酸钠20g/L、乳酸30ml/L、丁二酸3g/L、柠檬酸三钠3g/L、光亮剂1ml/L(光亮剂成分为1,4-丁炔二醇510g/L，环氧氯丙烷150g/L，对甲苯磺酰胺3g/L，氢氧化钠30g/L)、硫脲0.5g/L，加入氨水调节pH值到4.4～4.6。化学镀完成后用清水洗净后烘干。将镀镍后的板栅置于氟硼酸体系电镀镀铅，电镀铅液成分为氟硼酸220ml/L、硼酸20g/L、醋酸铅180g/L、氟硼酸亚锡20g/L、明胶1g/L，硫脲0.2g/L，施镀温度40℃，按电流密度3Adm-2电镀6h，获得表面镀层为含锡量2.07％的铅锡合金镀铅层的铅酸蓄电池用轻型板栅。铝合金板栅的厚度为2mm，镀镍层厚度为40μm，铅锡合金镀层厚度为0.4mm。
实施例六：将方格状铝合金板栅置于化学镀镍液中，温度为88℃时化学镀1.5小时，化学镀镍液成分同实施例四。将镀镍后的板栅置于氟硼酸体系电镀镀铅，电镀铅液成分为氟硼酸190ml/L、硼酸18g/L、醋酸铅200g/L、氟硼酸亚锡30g/L、明胶1g/L，硫脲0.2g/L，施镀温度40℃，按电流密度3Adm-2电镀4h，获得表面镀层为含锡量为1.94％的铅锡合金镀铅层的铅酸蓄电池用轻型板栅。铝合金板栅的厚度为1.5mm，镀镍层厚度为30μm，铅锡合金镀层厚度为0.3mm。
实施例七：将网状铝合金板栅置于化学镀镍液中，温度为90℃时化学镀1.5小时，化学镀镍液成分为NiSO4·6H2O20g/L、次亚磷酸钠35g/L、乳酸15ml/L、丁二酸1g/L、柠檬酸三钠2g/L、光亮剂1ml/L(光亮剂成分为1,4-丁炔二醇450g/L，环氧氯丙烷160g/L，对甲苯磺酰胺4g/L，氢氧化钠35g/L)、氯化铅0.5g/L，加入氨水调节pH值到4.4～4.6。化学镀完成后用清水洗净后烘干。将镀镍后的板栅置于氟硼酸体系电镀镀铅，电镀铅液成分为氟硼酸200ml/L、硼酸15g/L、醋酸铅220g/L、明胶1g/L，硫脲0.2g/L，施镀温度40℃，按电流密度3Adm-2电镀7h，获得表面镀层为纯铅的铅酸蓄电池用轻型板栅。铝合金板栅的厚度为1.5mm，镀镍层厚度为40μm，镀铅层厚度为0.4mm。
Claims (8)
1.一种铅酸蓄电池用轻型板栅及其制备方法，其特征是，包括铝合金板栅(1)、采用电镀或化学镀方法镀在铝合金板栅表面的镀镍层(2)、采用电镀方法镀在镀镍层表面的镀铅层(3)。
2.根据权利要求1所述的一种铅酸蓄电池用轻型板栅及其制备方法，其特征是，所述铝合金板栅为网状板栅或辐射状板栅或方格状板栅。
3.根据权利要求1所述的一种铅酸蓄电池用轻型板栅及其制备方法，其特征是，所述采用电镀方法将镀镍层(2)镀在铝合金板栅(1)表面的技术参数为：电镀镍液成分为NiSO4·6H2O50～70g/L、柠檬酸三钠80～110g/L、H3BO35～8g/L、NaCl 8～10g/L、Na2SO435～45g/L、明胶0.3～0.5g/L，以铝合金板栅为阴极，单侧面积接近的镍板为阳极，施镀温度30～45℃，电流密度1～3Adm-2，电镀时间30min～50min。
4.根据权利要求1所述的一种铅酸蓄电池用轻型板栅及其制备方法，其特征是，所述采用化学镀方法将镀镍层(2)镀在铝合金板栅(1)表面的技术参数为：化学镀镍液成分为NiSO4·6H2O20～50g/L、次亚磷酸钠20～35g/L、乳酸15～30ml/L、丁二酸1～3g/L、柠檬酸三钠1～3g/L、光亮剂1ml/L、稳定剂0.5g/L，加入氨水调节pH值到4.4～4.6，施镀温度85℃～90℃，化学镀时间1h～2h。
5.根据权利要求4所述的一种铅酸蓄电池用轻型板栅及其制备方法，其特征是，所述光亮剂成分为1,4-丁炔二醇450～510g/L、环氧氯丙烷130～160g/L、对甲苯磺酰胺3～5g/L、氢氧化钠30～40g/L；稳定剂为次亚硫酸钠或硫脲或氯化铅。
6.根据权利要求1所述的一种铅酸蓄电池用轻型板栅及其制备方法，其特征是，所述镀铅层成分为纯铅或锡含量为0～5％的铅锡合金；镀铅层采用甲基磺酸体系或氟硼酸体系电镀方法获得；所述甲基磺酸体系电镀技术参数为：电镀铅液成分为甲基磺酸80～120ml/L、甲基磺酸铅150～200g/L、0～50g/L Sn2+、酒石酸钾钠2～5g/L、添加剂0.5～5g/L、pH＝1～1.5，施镀温度40℃，电流密度3Adm-2，电镀时间3～7h；所述氟硼酸体系电镀技术参数为：电镀铅液成分为氟硼酸190～220ml/L、硼酸15～20g/L、醋酸铅180～220g/L、氟硼酸亚锡0～30g/L、明胶1g/L、硫脲0.2g/L，施镀温度40℃，电流密度3Adm-2，电镀时间4～7h。
7.根据权利要求6所述的一种铅酸蓄电池用轻型板栅及其制备方法，其特征是，所述添加剂为聚乙二醇或对苯二酚。
8.根据权利要求1～7的任一项所述的一种铅酸蓄电池用轻型板栅及其制备方法，其特征是，所述铝合金板栅的厚度为1mm～2mm，镀镍层厚度为10μm～50μm，镀铅层厚度为0.1mm～0.5mm。
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| CN (1) | CN107069042A (zh) |
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| CN108130572A (zh) * | 2017-12-04 | 2018-06-08 | 陕西航空电气有限责任公司 | 一种铝合金预镀镍溶液 |
| CN108277482A (zh) * | 2018-02-01 | 2018-07-13 | 中国科学院宁波材料技术与工程研究所 | 宽窗口化学镀镍液及其镀覆方法 |
| CN109841837A (zh) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | 电镀法制备具有三维结构的铅炭电池板栅及制备和应用 |
| CN110923769A (zh) * | 2019-10-21 | 2020-03-27 | 肇庆理士电源技术有限公司 | 铅碳电池碳板栅薄铅镀层的电镀方法 |
| EP3598539A4 (en) * | 2017-12-11 | 2021-03-24 | Takasaki Denka Kougyousho Co., Ltd. | ELECTRODE BODY FOR LEAD ACCUMULATOR AND LEAD ACCUMULATOR USING SAME |
| CN112736366A (zh) * | 2020-12-29 | 2021-04-30 | 上海应用技术大学 | 一种铸焊轻型金属负极板栅铅蓄电池汇流排的方法 |
| CN116454524A (zh) * | 2023-05-31 | 2023-07-18 | 三一红象电池有限公司 | 一种防爆阀及其制备方法和应用 |
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| CN107665995A (zh) * | 2017-09-05 | 2018-02-06 | 超威电源有限公司 | 一种铅酸电池用铝基板栅及其制备方法、制备装置 |
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| CN109841837B (zh) * | 2017-11-28 | 2021-09-14 | 中国科学院大连化学物理研究所 | 电镀法制备具有三维结构的铅炭电池板栅及制备和应用 |
| CN108130572A (zh) * | 2017-12-04 | 2018-06-08 | 陕西航空电气有限责任公司 | 一种铝合金预镀镍溶液 |
| EP3598539A4 (en) * | 2017-12-11 | 2021-03-24 | Takasaki Denka Kougyousho Co., Ltd. | ELECTRODE BODY FOR LEAD ACCUMULATOR AND LEAD ACCUMULATOR USING SAME |
| US11342550B2 (en) | 2017-12-11 | 2022-05-24 | Hideaki Kato | Electrode body for lead-acid battery, lead-acid battery using the same, and method of manufacturing electrode body for lead-acid battery |
| CN108277482A (zh) * | 2018-02-01 | 2018-07-13 | 中国科学院宁波材料技术与工程研究所 | 宽窗口化学镀镍液及其镀覆方法 |
| CN110923769A (zh) * | 2019-10-21 | 2020-03-27 | 肇庆理士电源技术有限公司 | 铅碳电池碳板栅薄铅镀层的电镀方法 |
| CN110923769B (zh) * | 2019-10-21 | 2021-04-20 | 肇庆理士电源技术有限公司 | 铅碳电池碳板栅薄铅镀层的电镀方法 |
| CN112736366A (zh) * | 2020-12-29 | 2021-04-30 | 上海应用技术大学 | 一种铸焊轻型金属负极板栅铅蓄电池汇流排的方法 |
| CN116454524A (zh) * | 2023-05-31 | 2023-07-18 | 三一红象电池有限公司 | 一种防爆阀及其制备方法和应用 |
| CN116454524B (zh) * | 2023-05-31 | 2024-05-24 | 三一红象电池有限公司 | 一种防爆阀及其制备方法和应用 |
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