CN116666648A - Aluminum-based composite polar plate for high-capacity long-service-life lead-carbon energy storage battery and preparation method thereof - Google Patents
Aluminum-based composite polar plate for high-capacity long-service-life lead-carbon energy storage battery and preparation method thereof Download PDFInfo
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- CN116666648A CN116666648A CN202310759775.6A CN202310759775A CN116666648A CN 116666648 A CN116666648 A CN 116666648A CN 202310759775 A CN202310759775 A CN 202310759775A CN 116666648 A CN116666648 A CN 116666648A
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- Prior art keywords
- aluminum
- lead
- composite
- grid
- positive
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- 239000002131 composite material Substances 0.000 title claims abstract description 340
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 319
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 307
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 238000004146 energy storage Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 126
- 229910052709 silver Inorganic materials 0.000 claims abstract description 67
- 239000004332 silver Substances 0.000 claims abstract description 67
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 51
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract description 46
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 35
- 239000011505 plaster Substances 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000010410 layer Substances 0.000 claims description 217
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 82
- 238000007747 plating Methods 0.000 claims description 79
- 150000002910 rare earth metals Chemical class 0.000 claims description 79
- 229910000838 Al alloy Inorganic materials 0.000 claims description 77
- 230000007704 transition Effects 0.000 claims description 74
- 238000005406 washing Methods 0.000 claims description 68
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 229910018100 Ni-Sn Inorganic materials 0.000 claims description 51
- 229910018532 Ni—Sn Inorganic materials 0.000 claims description 51
- 239000000126 substance Substances 0.000 claims description 51
- 238000005452 bending Methods 0.000 claims description 50
- 239000008367 deionised water Substances 0.000 claims description 48
- 229910021641 deionized water Inorganic materials 0.000 claims description 48
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 claims description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 238000005260 corrosion Methods 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 36
- 229910052725 zinc Inorganic materials 0.000 claims description 36
- 239000011701 zinc Substances 0.000 claims description 36
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 33
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 31
- 244000060011 Cocos nucifera Species 0.000 claims description 31
- 239000011521 glass Substances 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000002386 leaching Methods 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 27
- 238000007254 oxidation reaction Methods 0.000 claims description 27
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 26
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 26
- 229910052791 calcium Inorganic materials 0.000 claims description 24
- 239000011575 calcium Substances 0.000 claims description 24
- 239000011324 bead Substances 0.000 claims description 22
- 239000003292 glue Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 20
- 239000000741 silica gel Substances 0.000 claims description 20
- 229910002027 silica gel Inorganic materials 0.000 claims description 20
- 238000003466 welding Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000000853 adhesive Substances 0.000 claims description 18
- 230000001070 adhesive effect Effects 0.000 claims description 18
- 239000011229 interlayer Substances 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000003575 carbonaceous material Substances 0.000 claims description 14
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 241000080590 Niso Species 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- 150000001721 carbon Chemical class 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000001632 sodium acetate Substances 0.000 claims description 10
- 235000017281 sodium acetate Nutrition 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 8
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 8
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 8
- YVIMHTIMVIIXBQ-UHFFFAOYSA-N [SnH3][Al] Chemical compound [SnH3][Al] YVIMHTIMVIIXBQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 claims description 5
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- JALQQBGHJJURDQ-UHFFFAOYSA-L bis(methylsulfonyloxy)tin Chemical compound [Sn+2].CS([O-])(=O)=O.CS([O-])(=O)=O JALQQBGHJJURDQ-UHFFFAOYSA-L 0.000 claims description 5
- TYMHOXOEBTYWAM-UHFFFAOYSA-L cobalt(2+);methanesulfonate Chemical compound [Co+2].CS([O-])(=O)=O.CS([O-])(=O)=O TYMHOXOEBTYWAM-UHFFFAOYSA-L 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 229920005610 lignin Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 3
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910020712 Co—Sb Inorganic materials 0.000 claims 1
- 229910000978 Pb alloy Inorganic materials 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- -1 calcium tin aluminum Chemical compound 0.000 description 12
- 230000007935 neutral effect Effects 0.000 description 12
- 238000007789 sealing Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000004005 microsphere Substances 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 230000008313 sensitization Effects 0.000 description 6
- 229940095064 tartrate Drugs 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000861 blow drying Methods 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 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 description 4
- 229940038773 trisodium citrate Drugs 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910000882 Ca alloy Inorganic materials 0.000 description 2
- 101100028920 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cfp gene Proteins 0.000 description 2
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 2
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- 229940026189 antimony potassium tartrate Drugs 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001999 grid alloy Substances 0.000 description 1
- 239000002141 low-antimony alloy Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
-
- 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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
-
- 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)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an aluminum-based composite polar plate for a high-capacity long-life lead-carbon energy storage battery and a preparation method thereof, and belongs to the technical field of energy storage batteries. The lead-carbon energy storage battery positive composite pole plate comprises a positive pole grid and positive lead plaster coated on the positive pole grid, and the lead-carbon energy storage battery negative composite pole plate comprises a negative pole grid and negative lead plaster coated on the negative pole grid; the positive grid comprises a grid type positive plate and a positive plate aluminum conductive beam, and the negative grid comprises a grid type negative plate and a negative plate aluminum conductive beam; the grid-type positive plate consists of an aluminum-based lead-cobalt-antimony rare earth/silver coated aluminum powder composite rod, and the grid-type negative plate consists of an aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod; compared with the traditional lead alloy grid, the tensile strength of the aluminum-based composite polar plate grid is improved by more than 50%, the polar plate conductivity is improved by more than 30%, and the high-current discharge performance is improved.
Description
Technical Field
The invention relates to an aluminum-based composite polar plate for a high-capacity long-life lead-carbon energy storage battery and a preparation method thereof, and belongs to the technical field of energy storage batteries.
Background
The lead-carbon battery is a capacitance type lead-acid battery, and active carbon is added into the negative electrode of the lead-acid battery, so that the problem of short cycle life of the traditional lead-acid battery is solved, and the service life of the lead-acid battery can be remarkably prolonged.
The lead-carbon battery is characterized in that a certain amount of active carbon and conductive carbon materials are doped into a negative plate of the lead-acid battery, so that the sulfation problem in the battery operation process is solved to the greatest extent, and the service life of the battery is effectively prolonged. However, the common active carbon is introduced into the negative electrode to greatly increase the hydrogen evolution current of the negative electrode, so that the water consumption is particularly serious in the use process of the battery, and finally the battery is invalid, and therefore, the problem of hydrogen evolution of the negative electrode of the lead-acid battery can be solved, and the lead-acid battery can comprehensively replace the lead-acid battery. The selection of the type of the carbon material, the combination of lead powder and the carbon material and the like become the bottleneck of improving the performance and commercialized popularization of the lead-carbon battery. Pb doping on the surface of the carbon material is a relatively effective hydrogen suppression method, and Pb powder cannot be doped into the pore structures by simple physical mixing, so that the doping depth and uniformity are poor, and the hydrogen suppression effect is limited.
In recent years, a plurality of novel technologies of lead-acid batteries, such as a novel structure, a corrosion-resistant lead alloy positive grid, a foam lead grid, a foam carbon grid, a novel negative electrode additive, a super lead-acid battery, a lead carbon battery, a bipolar ceramic diaphragm VRLA battery and the like, are developed. Aiming at the lead-based alloy for the grid, the grid alloy is subjected to the transformation from pure lead to high-antimony alloy and low-antimony alloy, and then to lead-calcium, lead-strontium, lead-tin and other antimony-free alloys to lead-silver-calcium, lead-calcium-strontium and other multi-element alloys through continuously modifying the alloy formula. Lead-silver-calcium alloy is the alloy adopted by most grids at present, and has excellent maintenance-free performance and electrochemical performance. However, the lead-silver-calcium alloy still cannot fully meet the demands of people due to the antimony-free effect and poor deep cycle performance.
Disclosure of Invention
Aiming at the problems of the electrode plate for the current lead-carbon energy storage battery, the invention provides the aluminum-based composite plate for the high-capacity long-service-life lead-carbon energy storage battery and the preparation method thereof, and the conductive beam adopts an aluminum plate, a cladding rod and a lead-clad aluminum composite structure and a symmetrical S-shaped grid, so that the weight of the battery is greatly reduced, the output power is improved, and the specific mass capacity of the battery is improved; the internal resistance of the battery is reduced, the conductivity is excellent, the current-guiding capability of the current collector is improved, and the distribution of current in the polar plate is improved, so that the utilization rate of electrode active substances is improved.
The aluminum-based composite polar plate for the high-capacity long-life lead carbon energy storage battery comprises a lead carbon energy storage battery positive composite polar plate and a lead carbon energy storage battery negative composite polar plate which are alternately arranged, wherein the lead carbon energy storage battery positive composite polar plate comprises a positive grid 1 and positive lead plaster coated and arranged on the positive grid 1, and the lead carbon energy storage battery negative composite polar plate comprises a negative grid 2 and negative lead plaster coated and arranged on the negative grid 2;
the positive grid 1 comprises a grid type positive plate and a positive plate aluminum conductive beam 12 arranged at the top end of the grid type positive plate, and the negative grid 2 comprises a grid type negative plate and a negative plate aluminum conductive beam 22 arranged at the top end of the grid type negative plate; the grid-type positive plate consists of an aluminum-based lead-cobalt-antimony rare earth/silver coated aluminum powder composite rod 11, and the grid-type negative plate consists of an aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod 21;
positive plate aluminum conductive beam 12 top is fixed to be provided with anodal ear 13, and the top of negative pole aluminum conductive beam is fixed to be provided with negative pole ear 23, and anodal ear 13 is connected through positive L type aluminium bar that converges, and negative pole ear 23 is connected through negative L type aluminium bar that converges, and positive L type aluminium bar that converges and negative L type aluminium bar's end all is provided with the copper aluminium composite conductor head of external power cord.
The aluminum-based lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite rod 11 sequentially comprises an aluminum or aluminum alloy rod, a Ni-Sn/rare earth composite transition layer, a lead-calcium-tin-aluminum intermediate layer and a lead-cobalt-antimony-rare earth/silver-coated aluminum powder active layer from inside to outside, and the aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod 21 sequentially comprises an aluminum or aluminum alloy rod and Ni-TiB from inside to outside 2 In composite transition layer, pb-Ca-AlAn interlayer and an outer layer of lead tin antimony/zirconium dioxide particles.
Preferably, the section of the aluminum or aluminum alloy rod in the aluminum-based lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite rod 11 is rectangular, the tooth depth is 0.1-0.3 mm, the tooth width is 0.05-0.3 mm, the diameter of the aluminum or aluminum alloy rod is 0.5-6.0 mm, the thickness of the Ni-Sn/rare earth composite transition layer is 1-10 mu m, the thickness of the lead-calcium-tin-aluminum intermediate layer is 0.5-6.0 mm, and the thickness of the lead-cobalt-antimony-rare earth/silver-coated aluminum powder active layer is 0.1-1.0 mm; the section of the aluminum or aluminum alloy rod in the aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod 21 is rectangular, the tooth depth is 0.05-0.2 mm, the tooth width is 0.05-0.2 mm, the diameter of the aluminum or aluminum alloy rod is 0.5-4.0 mm, and the Ni-TiB 2 The thickness of the composite transition layer is 1-10 mu m, the thickness of the lead-calcium-aluminum intermediate layer is 0.5-4.0 mm, and the thickness of the lead-tin-antimony/zirconium dioxide outer layer is 0.1-0.5 mm.
The rare earth of the Ni-Sn/rare earth composite transition layer in the aluminum-based lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite rod 11 is CeO 2 、La 2 O 3 Or Nd 2 O 3 The doping amount of rare earth is 0.05 to 0.5wt percent; the content of calcium in the lead-calcium tin-aluminum interlayer is 0.04 to 0.1wt percent, the content of tin is 0.1 to 0.6wt percent, and the content of aluminum is 0.01 to 0.05wt percent; the rare earth in the lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer is Ce, nd, pr or La, the cobalt content is 0.01-0.2 wt%, the antimony content is 0.05-0.5 wt%, the rare earth content is 0.01-0.2 wt%, the silver-coated aluminum powder content is 0.2-2 wt%, and the silver content of the silver-coated aluminum powder is 5-25 wt%;
Ni-TiB in aluminum-based lead tin antimony/zirconium dioxide particle composite rod 21 2 TiB of composite transition layer 2 The doping amount is 0.1-1 wt%, the calcium content in the lead-calcium-aluminum intermediate layer is 0.05-0.12 wt%, the aluminum content is 0.01-0.1 wt%, and the rest is lead; the tin content in the lead tin antimony/zirconium dioxide outer layer is 0.5-2.0 wt%, the antimony content is 0.1-1 wt%, and the zirconium dioxide content is 0.5-5 wt%.
The grid type positive plate comprises a positive grid frame and positive symmetrical S-shaped plate grid ribs, and the grid type negative plate comprises a negative grid frame and negative symmetrical S-shaped plate grid ribs.
The positive plate aluminum conductive beam 12 and the negative plate aluminum conductive beam 22 sequentially comprise an aluminum or aluminum alloy matrix, a hard anodic oxidation film layer, an anti-corrosion PTFE composite modified primer layer and a silica gel adhesive metal glue anti-corrosion layer from inside to outside.
Preferably, the thickness of the hard anodic oxidation film layer is 20-50 mu m, the thickness of the anticorrosive PTFE composite modified primer layer is 20-100 mu m, and the thickness of the anticorrosive layer of the silica gel adhesive metal glue is 40-200 mu m.
The preparation method of the positive plate aluminum conductive beam comprises the following specific steps:
(1) Sequentially performing alkali washing, oil removing and deionized water washing on the aluminum conductive beam by using a NaOH solution to obtain a pretreated aluminum conductive beam;
(2) Placing the pretreated aluminum conductive beam in a modified sulfuric acid solution for hard anodic oxidation, cleaning by deionized water, placing in hot water for sealing, blow-drying, and then placing in a vacuum at 400-600 ℃ for heat treatment for 0.5-2 h to obtain a hard anodic oxidation film layer;
(3) Immersing the aluminum conductive beam coated with the hard anodic oxidation film layer into modified PTFE emulsion with the temperature of 60-120 ℃ to be coated for 2-10 min to obtain an anti-corrosion PTFE composite modified primer layer;
(4) And coating the commercial silica gel adhesive metal glue on the surface of the aluminum conductive beam coated with the anti-corrosion PTFE composite modified primer layer at the temperature of 70-120 ℃ and curing for 1-3 hours to obtain the silica gel adhesive metal glue anti-corrosion layer.
The modified sulfuric acid solution contains 200-300 g/L sulfuric acid, 16-30 ml/L glycerin, 10-30 g/L oxalic acid and 10-30 g/L aluminum sulfate; the temperature of the hard anodic oxidation is 0.5-5 ℃, and the current density is 0.5-4A/dm 2 The tank voltage is 30-60V, and the oxidation time is 1-4 h after the stirring by bottom blowing.
75-90% of lead powder and 75-90% of hollow glass bead/MnO (mass of positive electrode lead paste) based on 100% of positive electrode lead paste 2 1.0 to 4.0 percent, tetrabasic lead sulfate powder 1.0 to 2.0 percent, colloidal graphite 0.1 to 0.8 percent, short fiber 0.1 to 0.2 percent, silicon dioxide 0.5 to 1.5 percent, sulfuric acid solution 6.0 to 11.5 percent and H 2 9.0 to 13.0 percent of O; 75-85% of lead powder and 75-85% of colloidal graphite based on 100% of negative electrode lead paste
0.2 to 1.0 percent and 0.5 to 5 percent of modified carbon material composite powder0.0 percent, 0.3 to 1.0 percent of superfine barium sulfate, 0.1 to 0.5 percent of lignin, 0.1 to 0.2 percent of short fiber, 6.0 to 9.0 percent of sulfuric acid solution and H 2 9-14% of O; the thickness of the positive electrode lead plaster layer is 5-9 mm, and the thickness of the negative electrode lead plaster layer is 4-7 mm.
Preferably, the hollow glass microsphere/MnO 2 Middle MnO 2 The content of (2) is 10-20 wt.%;
hollow glass bead/MnO 2 The preparation method comprises the following specific steps:
(1) Sequentially carrying out surface roughening, sensitization and activation treatment on the hollow glass beads to obtain activated hollow glass beads;
(2) Activated hollow glass beads are placed in Mn (NO) 3 ) 2 Soaking in absolute ethanol solution for 5-20 min, and sintering at 100-400 deg.c for 10-30 min; repeatedly soaking and sintering for 4-8 times to obtain the active hollow glass microsphere/MnO 2 。
The modified carbon material composite powder is coconut shell active carbon chemical plating lead-tin alloy, wherein the lead content in the coconut shell active carbon chemical plating lead-tin alloy is 10-20 wt.%, and the tin content is 10-20 wt.%;
the preparation method of the coconut shell active carbon chemical plating lead-tin alloy comprises the following specific steps:
(1) Coarsening, sensitizing and activating the coconut shell activated carbon in sequence to obtain activated coconut shell activated carbon;
(2) The activated coconut shell activated carbon is placed in neutral chemical plating lead-tin alloy liquid, and chemical plating is carried out for 1-3 hours at the temperature of 60-80 ℃ to obtain the coconut shell activated carbon chemical plating lead-tin alloy.
The neutral electroless lead-tin alloy plating solution contains PbC1 2 10～30g/L，SnC1 2 10 to 30g/L, 10 to 40g/L EDTA, 60 to 100g/L trisodium citrate, 10 to 40g/L nitrilotriacetic acid and TiC1 3 (50%) 10-40 mL/L; the pH value of the neutral electroless lead-tin alloy plating solution is 5-8.
The preparation method of the aluminum-based composite polar plate for the high-capacity long-life lead-carbon energy storage battery comprises the following specific steps:
s1, preparation of positive grid
Preparation of Ni-Sn/rare earth composite transition layer: sequentially carrying out alkali washing, deionized water washing, ultrasonic washing, primary zinc leaching, deionized water washing, nitric acid activation, deionized water washing, secondary zinc leaching, chemical composite plating of Ni-Sn/rare earth, deionized water washing and drying on aluminum or aluminum alloy to obtain a Ni-Sn/rare earth composite transition layer composite rod;
b. Preparing a lead-calcium tin-aluminum interlayer: placing the Ni-Sn/rare earth composite transition layer composite rod in a drawing coating extruder, and coating semi-molten lead-calcium-tin-aluminum alloy on the surface of the Ni-Sn/rare earth composite transition layer composite rod to obtain an aluminum-based/lead-calcium-tin-aluminum composite rod;
c. bending the aluminum-based/lead-calcium-tin-aluminum composite rod to form a positive grid frame and positive symmetric S-shaped plate grid ribs, and welding the positive grid frame and the positive symmetric S-shaped plate grid ribs to form a grid-shaped positive plate; the specific method comprises the following steps: after the aluminum base/lead calcium tin aluminum composite rod is calibrated, the calibration point is taken as an arc vertex, and the aluminum base/lead calcium tin aluminum composite rod is bent twice according to R=20-30 mm to form a positive grid frame, and the straight rods at the two ends of the arc form a right angle; bending according to R=8-30 mm in a two-dimensional plane by taking a calibration point as an arc according to the calibration length of 20-60 mm of the bending point spacing of the aluminum-based/lead-calcium-tin-aluminum composite rod, alternately bending forward and backward, wherein the included angle between straight rods at two ends of the arc is 105-130 degrees, and setting the contact position of the bending rod and the bottom of the frame as an arc with radius R=10-40 mm by taking the calibration point as the arc vertex according to the calibration length of 50-80 mm of the bending point spacing;
d. welding a positive aluminum conductive beam on the top end of a grid type positive plate, and placing the positive aluminum conductive beam in methylsulfonic acid liquid A to electroplate a lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite layer to obtain a positive grid;
e. Coating the positive lead plaster on a positive grid, and curing and drying to obtain a positive composite polar plate of the lead-carbon energy storage battery;
s2, preparation of negative grid
a.Ni-TiB 2 Preparation of a composite transition layer: sequentially performing alkaline washing, deionized water washing, ultrasonic washing, primary zinc leaching, deionized water washing, nitric acid activation, deionized water washing, secondary zinc leaching and chemical composite plating of Ni-TiB on aluminum or aluminum alloy 2 Washing with deionized water, dryingDrying to obtain Ni-TiB 2 A composite transition layer composite rod;
b. preparing a lead-calcium-aluminum interlayer: ni-TiB 2 The composite transition layer composite rod is placed in a drawing coating extruder for heat treatment for 5 to 10 minutes at the temperature of 120 to 300 ℃ and is coated with semi-molten lead-calcium aluminum alloy in Ni-TiB 2 The surface of the composite rod of the composite transition layer is provided with an aluminum-based/lead-calcium-aluminum composite rod;
c. bending the aluminum-based/lead-calcium-aluminum composite rod to form a negative grid frame and negative symmetrical S-shaped plate grid ribs, and welding the negative grid frame and the negative symmetrical S-shaped plate grid ribs to form a grid-type negative plate; the specific method comprises the following steps: after the aluminum-based/lead-calcium-aluminum composite rod is calibrated, the calibration point is taken as an arc vertex, the aluminum-based/lead-calcium-aluminum composite rod is bent twice according to R=20-30 mm to form a negative grid frame, and right angles are formed between the straight rods at the two ends of the arc; bending according to R=8-30 mm in a two-dimensional plane by taking a calibration point as an arc according to the calibration length of 20-60 mm of the bending point spacing of the aluminum-based/lead-calcium-aluminum composite rod, alternately bending forward and backward, wherein the included angle between straight rods at two ends of the arc is 105-130 degrees, and setting the contact position of the bending rod and the bottom of the frame as an arc with radius R=10-40 mm by taking the calibration point as the arc vertex according to the calibration length of 50-80 mm of the bending point spacing;
d. Welding a negative aluminum conductive beam on the top end of a grid-type negative plate, and placing the negative aluminum conductive beam in methylsulfonic acid liquid B to electroplate a lead-tin-antimony/zirconium dioxide composite layer to obtain a negative grid;
e. and (3) coating the negative electrode lead plaster on a negative electrode grid, and curing and drying to obtain the negative electrode composite polar plate of the lead-carbon energy storage battery.
The zinc leaching solution contains 200-400 g/L of NaOH, 50-100 g/L of ZnO, 5-20 g/L of potassium sodium tartrate, and the zinc leaching temperature is 20-40 ℃ and the time is 30-100S;
the plating solution for chemically plating Ni-Sn/rare earth contains NiSO 4 ·7H 2 O 25～45g/L，SnC1 4 5～15g/L，NaHPO 2 10-30 g/L, 10-30 g/L of sodium acetate, 1-10 ml/L of glacial acetic acid, 1-10 g/L of rare earth, the pH value of plating solution is 4.4-5.0, the temperature of chemical composite plating Ni-Sn/rare earth is 80-95 ℃, and the traction speed is 2-8m/min;
the methylsulfonic acid liquid A contains methylsulfonic acid80-200 g/L of lead acid, 8-24 g/L of cobalt methylsulfonate, 4-12 g/L of potassium antimony tartrate and nano CeO 2 4-20 g/L, and 2-10 g/L of silver-coated aluminum powder; the anode of the electroplated lead-cobalt-antimony rare earth/silver coated aluminum powder composite layer is an as-cast pure lead plate, the temperature is 30-60 ℃, and the current density is 0.5-4A/dm 2 The time is 1-6 h;
the chemical composite plating Ni-TiB 2 The plating solution of (C) contains NiSO 4 ·7H 2 40-100 g/L of O, 10-30 g/L of hydrazine hydrate, 10-30 g/L of sodium acetate and nano TiB 2 2-12 g/L, pH value of plating solution is 9-10, and Ni-TiB is chemically plated 2 The temperature of the belt is 80-95 ℃ and the traction speed is 2-8 m/min;
the methylsulfonic acid liquid B contains 40-120 g/L of lead methylsulfonate, 10-30 g/L of stannous methylsulfonate, 2-8 g/L of antimony potassium tartrate and nano ZrO 2 4-20 g/L, 0.1-0.5 g/L o-chlorobenzaldehyde; the anode of the electroplated lead-tin-antimony/zirconium dioxide composite layer is an as-cast pure lead plate, the temperature is 30-60 ℃, and the current density is 0.5-4A/dm 2 The time is 1-6 h.
The beneficial effects of the invention are as follows:
(1) Compared with the traditional lead alloy grid, the lead-carbon energy storage battery positive composite pole plate and the lead-carbon energy storage battery negative composite pole plate have the advantages that the deformation resistance and creep resistance are high, the tensile strength is improved by 50%, the pole plate conductivity is improved by 30%, the heavy-current discharge performance is improved, and the heavy metal lead consumption is reduced by more than 40%;
(2) Compared with lead alloy, aluminum has light weight, excellent conductive performance and light weight, but aluminum and the alloy thereof are relatively active, and are directly used as conductive beams, and are easy to react with acid mist sulfuric acid to generate sulfate crystallization in the use process, so that the cathode and the anode are easy to be short-circuited; the aluminum conductive beam hard anodic oxidation improves the strength and corrosion resistance of aluminum, increases the surface porosity, is favorable for subsequent surface coating treatment, and adopts corrosion-resistant polytetrafluoroethylene and silica gel adhesive metal glue double-layer protection, so that the surface of the aluminum beam is well protected, and a large amount of aluminum sulfate crystal salt cannot be generated due to exposure of aluminum in the electrolytic process;
(3) The manufacturing of the positive and negative electrode composite rod can adopt full-automatic line production, the mechanization degree is high, the labor cost can be saved, the efficiency is improved, the standardization degree is high, the manufactured grid has good consistency, the consistency of charging and discharging of the positive and negative electrodes in use is ensured, and the current efficiency is improved;
(4) The invention adopts Ni-Sn-rare earth and Ni-TiB with harder surface chemical plating and high heat resistance of aluminum bar 2 The compactness of the composite coating is improved, and a support is provided for the lead alloy which is softer in the follow-up extrusion drawing, so that the composite is tightly and firmly promoted, and the prepared composite rod has good stability;
(5) The invention prepares the lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite coating by composite electrodeposition in the methylsulfonate by utilizing the good electrocatalytic activity of cobalt and the conductivity and the catalytic activity of silver-coated aluminum, thereby greatly improving the conductivity and the discharge capacity of the anode;
(6) The invention adds hollow glass microsphere/MnO with catalytic activity into the positive electrode lead plaster 2 The composite particles are beneficial to improving the discharge current of the battery; the lead-tin alloy coating coated by the coconut shell activated carbon is added into the negative lead plaster, so that the sulfation problem in the battery operation process is eliminated, and the hydrogen evolution problem of the activated carbon is solved.
Drawings
FIG. 1 is a schematic structural view of a positive grid;
FIG. 2 is a schematic view of a negative grid structure;
FIG. 3 is a schematic cross-sectional view of the composite rod of FIG. 1;
FIG. 4 is a schematic cross-sectional view of the composite rod of FIG. 2;
FIG. 5 is a schematic cross-sectional view of the positive conductive beam of FIG. 1;
FIG. 6 is a schematic cross-sectional view of the negative conductive beam of FIG. 2;
in the figure: 1-positive grid, 2-negative grid, 11-aluminum-based lead-cobalt-antimony rare earth/silver coated aluminum powder composite rod; 12-positive plate aluminum conductive beams; 13-positive electrode lugs; 21-aluminum-based lead tin antimony/zirconium dioxide particle composite rod; 22-negative plate aluminum conductive beams; 23-negative electrode ear; 111-a positive aluminum or aluminum alloy composite rod; 112-Ni-Sn/rare earth composite transition layer; 113-lead calcium tin aluminum interlayer; 114-lead cobalt antimony rare earth/silver coated aluminum powder active layer;211-a negative electrode aluminum or aluminum alloy composite rod; 212-Ni-TiB 2 A composite transition layer; 213-lead calcium aluminum interlayer; 214-lead tin antimony/zirconium dioxide particle outer layer; 121-positive electrode conductivity Liang Lvji; 122-a hard anodic oxidation film layer of the positive conductive beam; 123-positive electrode conductive Liang Fangfu PTFE composite modified primer layer; 124-positive electrode conductive Liang Guijiao is adhered with a metal glue anti-corrosion layer; 221-negative electrode conductivity Liang Lvji; 222-anode conductive Liang Ying anode oxide film; 223-negative electrode conductive Liang Fangfu PTFE composite modified primer layer; 224-negative electrode conductive Liang Guijiao is adhered with a metal glue anti-corrosion layer.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Summary of the invention
The aluminum-based composite polar plate for the high-capacity long-life lead carbon energy storage battery comprises a lead carbon energy storage battery positive composite polar plate and a lead carbon energy storage battery negative composite polar plate which are alternately arranged, wherein the lead carbon energy storage battery positive composite polar plate comprises a positive grid 1 and positive lead plaster coated and arranged on the positive grid 1, and the lead carbon energy storage battery negative composite polar plate comprises a negative grid 2 and negative lead plaster coated and arranged on the negative grid 2;
the positive grid 1 comprises a grid-type positive plate and a positive plate aluminum conductive beam 12 (see fig. 1) arranged at the top end of the grid-type positive plate, and the negative grid 2 comprises a grid-type negative plate and a negative plate aluminum conductive beam 22 (see fig. 2) arranged at the top end of the grid-type negative plate; the grid-type positive plate consists of an aluminum-based lead-cobalt-antimony rare earth/silver coated aluminum powder composite rod 11, and the grid-type negative plate consists of an aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod 21;
the top end of the positive plate aluminum conductive beam 12 is fixedly provided with a positive electrode lug 13, the top end of the negative electrode aluminum conductive beam is fixedly provided with a negative electrode lug 23, the positive electrode lug 13 is connected through a positive confluence L-shaped aluminum bar, the negative electrode lug 23 is connected through a negative confluence L-shaped aluminum bar, and the ends of the positive confluence L-shaped aluminum bar and the negative confluence L-shaped aluminum bar are respectively provided with a copper-aluminum composite conductive head externally connected with a power line;
The aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 sequentially comprises aluminum or aluminum from inside to outsideThe alloy rod, the Ni-Sn/rare earth composite transition layer, the lead-calcium-tin-aluminum intermediate layer and the lead-cobalt-antimony rare earth/silver coated aluminum powder active layer (see figure 3), the aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod 21 sequentially comprises aluminum or aluminum alloy rods and Ni-TiB from inside to outside 2 A composite transition layer, a lead calcium aluminum intermediate layer and a lead tin antimony/zirconium dioxide particle outer layer (see figure 4);
the grid-type positive plate comprises a positive grid frame and positive symmetrical S-shaped plate grid ribs, and the grid-type negative plate comprises a negative grid frame and negative symmetrical S-shaped plate grid ribs;
the positive plate aluminum conductive beam 12 and the negative plate aluminum conductive beam 22 sequentially comprise an aluminum or aluminum alloy matrix, a hard anodic oxidation film layer, an anti-corrosion PTFE composite modified primer layer and a silica gel adhesive metal glue anti-corrosion layer from inside to outside;
the positive composite polar plate of the lead-carbon energy storage battery and the negative composite polar plate of the lead-carbon energy storage battery have strong deformation resistance and creep resistance, and compared with the traditional lead alloy grid, the tensile strength is improved by 50%, the polar plate conductivity is improved by 30%, the heavy-current discharge performance is improved, and the heavy metal lead consumption is reduced by more than 40%.
Example 1: an aluminum-based composite polar plate (see fig. 1-6) for a high-capacity long-life lead carbon energy storage battery comprises a lead carbon energy storage battery positive composite polar plate and a lead carbon energy storage battery negative composite polar plate which are alternately arranged, wherein the lead carbon energy storage battery positive composite polar plate comprises a positive polar plate grid 1 and positive lead plaster coated on the positive polar plate grid 1, and the lead carbon energy storage battery negative composite polar plate comprises a negative polar plate grid 2 and negative lead plaster coated on the negative polar plate grid 2;
The positive grid 1 comprises a grid type positive plate and a positive plate aluminum conductive beam 12 arranged at the top end of the grid type positive plate, and the negative grid 2 comprises a grid type negative plate and a negative plate aluminum conductive beam 22 arranged at the top end of the grid type negative plate; the grid-type positive plate consists of an aluminum-based lead-cobalt-antimony rare earth/silver coated aluminum powder composite rod 11, and the grid-type negative plate consists of an aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod 21;
the top end of the positive plate aluminum conductive beam 12 is fixedly provided with a positive electrode lug 13, the top end of the negative electrode aluminum conductive beam is fixedly provided with a negative electrode lug 23, the positive electrode lug 13 is connected through a positive confluence L-shaped aluminum bar, the negative electrode lug 23 is connected through a negative confluence L-shaped aluminum bar, and the ends of the positive confluence L-shaped aluminum bar and the negative confluence L-shaped aluminum bar are respectively provided with a copper-aluminum composite conductive head externally connected with a power line;
the aluminum-based lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite rod 11 sequentially comprises an aluminum rod, a Ni-Sn/rare earth composite transition layer, a lead-calcium-tin-aluminum intermediate layer and a lead-cobalt-antimony-rare earth/silver-coated aluminum powder active layer from inside to outside, and the aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod 21 sequentially comprises an aluminum rod and Ni-TiB from inside to outside 2 The composite transition layer, the lead-calcium-aluminum intermediate layer and the lead-tin-antimony/zirconium dioxide particle outer layer; the section of the aluminum rod in the aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 is rectangular, the tooth depth is 0.2mm, the tooth width is 0.15mm, the diameter of the aluminum rod is 4.0mm, the thickness of the Ni-Sn/rare earth composite transition layer is 5 mu m, the thickness of the lead-calcium-tin-aluminum intermediate layer is 3.0mm, and the thickness of the lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer is 0.5mm; the section of the aluminum bar in the aluminum-based lead-tin-antimony/zirconium dioxide particle composite bar 21 is rectangular, the tooth depth is 0.1mm, the tooth width is 0.1mm, the diameter of the aluminum bar is 2.5mm, and the Ni-TiB is 2 The thickness of the composite transition layer is 5 mu m, the thickness of the lead-calcium-aluminum intermediate layer is 2.0mm, and the thickness of the lead-tin-antimony/zirconium dioxide outer layer is 0.3mm;
the rare earth of the Ni-Sn/rare earth composite transition layer in the aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod 11 is La 2 O 3 The rare earth doping amount is 0.3wt.%; the lead-calcium-tin-aluminum interlayer has a calcium content of 0.065wt.%, a tin content of 0.4wt.%, and an aluminum content of 0.025wt.%; the rare earth in the lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer is Ce, the cobalt content is 0.1wt.%, the antimony content is 0.3wt.%, the rare earth content is 0.1wt.%, the silver-coated aluminum powder content is 1.2wt.%, and the silver content of the silver-coated aluminum powder is 20wt.%;
Ni-TiB in aluminum-based lead tin antimony/zirconium dioxide particle composite rod 21 2 TiB of composite transition layer 2 The doping amount is 0.5wt.%, the calcium content in the lead-calcium-aluminum intermediate layer is 0.08wt.%, the aluminum content is 0.05wt.%, and the rest is lead; the tin content in the lead tin antimony/zirconium dioxide outer layer is 1.0wt.%, the antimony content is 0.5wt.%, and the zirconium dioxide content is 2.5wt.%;
the grid-type positive plate comprises a positive grid frame and positive symmetrical S-shaped plate grid ribs, and the grid-type negative plate comprises a negative grid frame and negative symmetrical S-shaped plate grid ribs;
the positive plate aluminum conductive beam 12 (see fig. 5) and the negative plate aluminum conductive beam 22 (see fig. 6) sequentially comprise an aluminum matrix, a hard anodic oxidation film layer, an anti-corrosion PTFE composite modified primer layer and a silica gel adhesive metal glue anti-corrosion layer from inside to outside; the thickness of the positive aluminum conductive beam is 12mm, and the thickness of the negative aluminum conductive beam is 10mm;
The thickness of the hard anodic oxidation film layer is 35 mu m, the thickness of the anti-corrosion PTFE composite modified primer layer is 60 mu m, and the thickness of the anti-corrosion layer of the silica gel adhesive metal glue is 100 mu m;
the preparation method of the positive plate aluminum conductive beam comprises the following specific steps:
(1) Sequentially carrying out alkaline washing and oil removal and deionized water washing on the aluminum conductive beam by using a NaOH solution with the concentration of 15wt.% to obtain a pretreated aluminum conductive beam;
(2) Placing the pretreated aluminum conductive beam in modified sulfuric acid solution at 2deg.C with current density of 2A/dm 2 Carrying out hard anodic oxidation for 2 hours under the condition of 50V tank voltage and bottom blowing stirring, cleaning by deionized water, sealing in hot water, blow-drying, and carrying out vacuum heat treatment at 500 ℃ for 1.5 hours to obtain a hard anodic oxidation film layer; the modified sulfuric acid solution contains 250g/L sulfuric acid, 20ml/L glycerin, 20g/L oxalic acid and 20g/L aluminum sulfate;
(3) Immersing the aluminum conductive beam coated with the hard anodic oxidation film layer into modified PTFE emulsion at 90 ℃ for coating for 6min to obtain an anti-corrosion PTFE composite modified primer layer;
(4) Coating commercial silica gel adhesive metal glue on the surface of an aluminum conductive beam coated with an anti-corrosion PTFE composite modified primer layer at the temperature of 100 ℃ and curing for 2 hours to obtain a silica gel adhesive metal glue anti-corrosion layer;
80% of lead powder and 80% of hollow glass beads/MnO (metal oxide nitride) by taking the mass of the positive electrode lead paste as 100% 2 2.0%, tetrabasic lead sulfate powder 1.5%, colloidal graphite 0.6%, short fiber 0.15%, silicon dioxide 1.0%, sulfuric acid solution 9%, H 2 O11%; 80% of lead powder, 0.6% of colloid graphite and modified carbon material composite powder based on 100% of the mass of the negative electrode lead plasterEnd 2.5%, superfine barium sulfate 0.6%, lignin 0.3%, short fiber 0.15%, sulfuric acid solution 7.5%, H 2 O11%; the thickness of the positive electrode lead plaster layer is 7mm, and the thickness of the negative electrode lead plaster layer is 5mm;
hollow glass bead/MnO 2 Middle MnO 2 Is present in an amount of 15wt.%; hollow glass bead/MnO 2 The preparation method comprises the following specific steps:
(1) Coarsening the hollow glass beads by 10g/LKF and 10g/L SnC1 2 +10ml/L hydrochloric acid sensitization, 4g/LAgNO 3 Carrying out solution activation treatment to obtain activated hollow glass microspheres;
(2) The activated hollow glass beads were placed in a concentration of 20wt.% Mn (NO 3 ) 2 Soaking in absolute ethanol solution for 10min, and sintering at 200deg.C for 20min; repeatedly soaking and sintering for 6 times to obtain active hollow glass microsphere/MnO 2 ；
The modified carbon material composite powder is coconut shell active carbon chemical plating lead-tin alloy, wherein the lead content in the coconut shell active carbon chemical plating lead-tin alloy is 15wt.%, and the tin content is 15wt.%;
The preparation method of the coconut shell active carbon chemical plating lead-tin alloy comprises the following specific steps:
(1) Coarsening coconut shell activated carbon by 10g/LKF and 10g/L SnC1 2 +10ml/L hydrochloric acid sensitization, 1g/L PdC1 2 Carrying out solution activation treatment to obtain activated coconut shell activated carbon;
(2) Placing activated coconut shell activated carbon into neutral chemical plating lead-tin alloy liquid, and performing chemical plating at 70 ℃ for 2 hours to obtain the coconut shell activated carbon chemical plating lead-tin alloy; the neutral electroless lead-tin alloy plating solution contains PbCl 2 20g/L，SnCl 2 20g/L, EDTA 25g/L, trisodium citrate 80g/L, nitrilotriacetic acid 25g/L, tiC1 3 (50%) 25mL/L; the pH value of the neutral electroless lead-tin alloy plating liquid is 7;
the preparation method of the aluminum-based composite polar plate for the high-capacity long-life lead-carbon energy storage battery comprises the following specific steps:
s1, preparation of positive grid
Preparation of Ni-Sn/rare earth composite transition layer: sequentially carrying out alkali washing, deionized water washing, ultrasonic washing, primary zinc leaching, deionized water washing, nitric acid activation, deionized water washing, secondary zinc leaching, chemical composite plating of Ni-Sn/rare earth, deionized water washing and drying on an aluminum bar to obtain a Ni-Sn/rare earth composite transition layer composite bar;
the zinc leaching solution contains 300g/L of NaOH, 70g/L of ZnO, 12g/L of potassium sodium tartrate, and the zinc leaching temperature is 30 ℃ and the time is 60S;
The plating solution for chemically plating Ni-Sn/rare earth contains NiSO 4 ·7H 2 O 35g/L，SnC1 4 10g/L，NaHPO 2 20g/L of sodium acetate, 20g/L of glacial acetic acid, 6ml/L of rare earth, 5g/L of rare earth, 4.7 pH value of plating solution, 90 ℃ of chemical composite plating Ni-Sn/rare earth, and 6m/min of traction speed;
b. preparing a lead-calcium tin-aluminum interlayer: placing the Ni-Sn/rare earth composite transition layer composite rod in a drawing coating extruder, and coating semi-molten lead-calcium-tin-aluminum alloy on the surface of the Ni-Sn/rare earth composite transition layer composite rod to obtain an aluminum-based/lead-calcium-tin-aluminum composite rod;
c. bending the aluminum-based/lead-calcium-tin-aluminum composite rod to form a positive grid frame and positive symmetric S-shaped plate grid ribs, and welding the positive grid frame and the positive symmetric S-shaped plate grid ribs to form a grid-shaped positive plate; the specific method comprises the following steps: after the aluminum base/lead calcium tin aluminum composite rod is calibrated, the calibration point is taken as an arc vertex, the aluminum base/lead calcium tin aluminum composite rod is bent twice according to R=25mm to form a positive grid frame, and right angles are formed between the straight rods at the two ends of the arc; bending according to R=20mm in a two-dimensional plane by taking a calibration point as an arc according to the calibration length of 40mm of the bending point spacing of the aluminum-based/lead-calcium-tin-aluminum composite rod, bending alternately in the forward direction and the reverse direction, wherein the included angle between straight rods at two ends of the arc is 115 degrees, and the contact position between the bending rod and the bottom of the frame is set into an arc with radius R=30mm by taking the calibration point as the arc vertex according to the 60mm calibration length of the bending point spacing;
d. Welding positive aluminum conductive beam on top of grid type positive plate, placing in methylsulfonic acid solution A, taking cast pure lead plate as anode, and controlling current density at 45deg.C and 2A/dm 2 Electroplating a lead-cobalt-antimony rare earth/silver coated aluminum powder composite layer for 3 hours under mechanical stirring to obtain a positive grid; the methylsulfonic acid solution A contains methyl methacrylateLead (Pb (CH) 3 SO 3 ) 2 ) 120g/L, cobalt methylsulfonate (Co (CH) 3 SO 3 ) 2 ) 16g/L, 8g/L of potassium antimonate tartrate and nano CeO 2 12g/L, silver Bao Lvfen g/L;
e. coating the positive lead plaster on a positive grid, and curing and drying to obtain a positive composite polar plate of the lead-carbon energy storage battery;
s2, preparation of negative grid
a.Ni-TiB 2 Preparation of a composite transition layer: sequentially performing alkaline washing, deionized water washing, ultrasonic washing, primary zinc leaching, deionized water washing, nitric acid activation, deionized water washing, secondary zinc leaching and chemical composite plating of Ni-TiB on aluminum 2 Washing with deionized water and drying to obtain Ni-TiB 2 A composite transition layer composite rod;
the zinc leaching solution contains 300g/L of NaOH, 70g/L of ZnO, 12g/L of potassium sodium tartrate, and the zinc leaching temperature is 30 ℃ and the time is 60S;
chemical composite plating Ni-TiB 2 The plating solution of (C) contains NiSO 4 ·7H 2 70g/L of O, 20g/L of hydrazine hydrate, 20g/L of sodium acetate and nano TiB 2 7g/L, pH value of plating solution is 10, and Ni-TiB is plated by chemical combination 2 The temperature of (2) is 90 ℃, and the traction speed is 5m/min;
b. preparing a lead-calcium-aluminum interlayer: ni-TiB 2 The composite transition layer composite rod is placed in a drawing cladding extruder for heat treatment for 7min at 200 ℃, and the semi-molten lead-calcium aluminum alloy is clad on Ni-TiB 2 The surface of the composite rod of the composite transition layer is provided with an aluminum-based/lead-calcium-aluminum composite rod;
c. bending the aluminum-based/lead-calcium-aluminum composite rod to form a negative grid frame and negative symmetrical S-shaped plate grid ribs, and welding the negative grid frame and the negative symmetrical S-shaped plate grid ribs to form a grid-type negative plate; the specific method comprises the following steps: after the aluminum-based/lead-calcium-aluminum composite rod is calibrated, the calibration point is taken as an arc vertex, the aluminum-based/lead-calcium-aluminum composite rod is bent twice according to R=25mm to form a negative grid frame, and right angles are formed between straight rods at two ends of the arc; according to the calibration length of 40mm of the bending point spacing of the aluminum-based/lead-calcium-aluminum composite rod, bending according to R=20mm is laid on a two-dimensional plane by taking the calibration point as an arc, bending alternately in forward and reverse directions, wherein the included angle between straight rods at two ends of the arc is 115 degrees, the contact position between the bending rod and the bottom of the frame is set into an arc with radius R=30mm by taking the calibration point as the arc vertex according to the 60mm of the bending point spacing;
d. welding a negative aluminum conductive beam on the top end of a grid-type negative plate, placing the negative aluminum conductive beam in methylsulfonic acid liquid B, taking an as-cast pure lead plate as an anode, and controlling the current density to be 2A/dm at the temperature of 45 DEG C 2 Electroplating the lead-tin-antimony/zirconium dioxide composite layer for 3 hours under the condition of mechanical stirring to obtain a negative grid; the methylsulfonic acid solution B contains lead methylsulfonate (Pb (CH) 3 SO 3 ) 2 ) 80g/L, stannous methanesulfonate (Sn (CH) 3 SO 3 ) 2 ) 20g/L, 5g/L of potassium antimonate tartrate and nano ZrO 2 12g/L, 0.3g/L o-chlorobenzaldehyde;
e. coating negative lead plaster on a negative grid, and solidifying and drying to obtain a negative composite polar plate of the lead-carbon energy storage battery;
the battery assembly process comprises the following steps: the positive plate and the negative plate are both coated with separator paper on both sides, the negative electrode is a first sheet, then the positive electrode and the negative electrode are alternately laminated, the electrode group is of a 7 positive 8 negative structure, and the electrode group is clamped and pressed into the battery case; the battery is assembled after the sealing cover, the sealing and the air tightness detection, and finally the performance is tested;
the positive and negative plates manufactured by the composite grid of the embodiment have strong deformation resistance and creep resistance, and compared with the traditional lead-0.06% calcium-1.2% tin alloy grid, the tensile strength is improved by 90%, the plate conductivity is improved by 60%, the heavy current discharge performance is improved by 30%, and the heavy metal lead consumption is reduced by 60%.
Example 2: the aluminum-based composite polar plate for the high-capacity long-service-life lead carbon energy storage battery of the embodiment is basically the same as the grid structure of the aluminum-based composite polar plate of the embodiment 1, and is different in that:
The aluminum-based lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite rod 11 sequentially comprises an aluminum alloy rod (1060), a Ni-Sn/rare earth composite transition layer, a lead-calcium-tin-aluminum intermediate layer and a lead-cobalt-antimony-rare earth/silver-coated aluminum powder active layer from inside to outside, and the aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod 21 sequentially comprises an aluminum alloy rod (1050) and a Ni-TiB from inside to outside 2 The composite transition layer, the lead-calcium-aluminum intermediate layer and the lead-tin-antimony/zirconium dioxide particle outer layer; aluminum-based lead-cobalt-antimony rare earth/silver packageThe section of the aluminum alloy rod (1060) in the aluminum powder composite rod 11 is rectangular, the tooth depth is 0.1mm, the tooth width is 0.05mm, the diameter of the aluminum alloy rod (1060) is 2.5mm, the thickness of the Ni-Sn/rare earth composite transition layer is 1 mu m, the thickness of the lead-calcium-tin-aluminum intermediate layer is 0.5mm, and the thickness of the lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer is 0.1mm; the section of the aluminum alloy rod (1050) in the aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod 21 is rectangular, the tooth depth is 0.05mm, the tooth width is 0.05mm, the diameter of the aluminum alloy rod (1050) is 1.5mm, and the Ni-TiB is 2 The thickness of the composite transition layer is 1 mu m, the thickness of the lead-calcium-aluminum intermediate layer is 0.5mm, and the thickness of the lead-tin-antimony/zirconium dioxide outer layer is 0.1mm;
the rare earth of the Ni-Sn/rare earth composite transition layer in the aluminum-based lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite rod 11 is CeO 2 The rare earth doping amount is 0.05wt.%; the lead-calcium-tin-aluminum interlayer has a calcium content of 0.04wt.%, a tin content of 0.1wt.%, and an aluminum content of 0.01wt.%; the rare earth in the lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer is Nd, the cobalt content is 0.01wt.%, the antimony content is 0.05wt.%, the rare earth content is 0.01wt.%, the silver-coated aluminum powder content is 0.2wt.%, and the silver content of the silver-coated aluminum powder is 5wt.%;
Ni-TiB in aluminum-based lead tin antimony/zirconium dioxide particle composite rod 21 2 TiB of composite transition layer 2 The doping amount is 0.1wt.%, the calcium content in the lead-calcium-aluminum intermediate layer is 0.05wt.%, the aluminum content is 0.01wt.%, and the rest is lead; the tin content in the lead tin antimony/zirconium dioxide outer layer is 0.5wt.%, the antimony content is 0.1wt.%, and the zirconium dioxide content is 0.5wt.%;
the grid-type positive plate comprises a positive grid frame and positive symmetrical S-shaped plate grid ribs, and the grid-type negative plate comprises a negative grid frame and negative symmetrical S-shaped plate grid ribs;
the thickness of the anode aluminum alloy conductive beam is 6mm, the thickness of the cathode aluminum alloy conductive beam is 4mm, and the anode aluminum alloy conductive beam and the cathode aluminum alloy conductive beam sequentially comprise aluminum or an aluminum alloy matrix, a hard anodic oxidation film layer, an anti-corrosion PTFE composite modified primer layer and a silica gel metal glue anti-corrosion layer from inside to outside;
The thickness of the hard anodic oxidation film layer is 20 mu m, the thickness of the anti-corrosion PTFE composite modified primer layer is 20 mu m, and the thickness of the anti-corrosion layer of the silica gel adhesive metal glue is 40 mu m;
the preparation method of the positive plate aluminum alloy conductive beam comprises the following specific steps:
(1) Sequentially carrying out alkali washing and oil removal and deionized water washing on the aluminum alloy conductive beam by using a NaOH solution with the concentration of 10wt.% to obtain a pretreated aluminum alloy conductive beam;
(2) Placing the pretreated aluminum alloy conductive beam in modified sulfuric acid solution at 0.5deg.C and current density of 0.5A/dm 2 Carrying out hard anodic oxidation for 1h under the condition of 60V tank voltage and bottom blowing stirring, cleaning with deionized water, sealing in hot water, blow-drying, and carrying out vacuum heat treatment at 400 ℃ for 0.5h to obtain a hard anodic oxidation film layer; the modified sulfuric acid solution contains 200g/L sulfuric acid, 16ml/L glycerin, 10g/L oxalic acid and 10g/L aluminum sulfate;
(3) Immersing the aluminum alloy conductive beam coated with the hard anodic oxidation film layer into modified PTFE emulsion at 60 ℃ for coating for 2min to obtain an anti-corrosion PTFE composite modified primer layer;
(4) Coating commercial silica gel adhesive metal glue on the surface of an aluminum alloy conductive beam coated with an anti-corrosion PTFE composite modified primer layer at the temperature of 70 ℃ and curing for 1h to obtain a silica gel adhesive metal glue anti-corrosion layer;
75% of lead powder and 75% of hollow glass beads/MnO (total mass of the lead paste) based on 100% of the positive electrode lead paste 2 1.0 percent of tetrabasic lead sulfate powder, 1.0 percent of colloidal graphite, 0.1 percent of short fiber, 0.10 percent of silicon dioxide, 0.5 percent of sulfuric acid solution and 6.0 percent of H 2 O9.0%; based on 100% of the mass of the negative electrode lead plaster, 75% of lead powder, 0.2% of colloidal graphite, 0.5% of modified carbon material composite powder, 0.3% of superfine barium sulfate, 0.1% of lignin, 0.10% of short fiber, 6.0% of sulfuric acid solution and H 2 O9%; the thickness of the positive electrode lead plaster layer is 5mm, and the thickness of the negative electrode lead plaster layer is 4mm;
hollow glass bead/MnO 2 Middle MnO 2 The content of (2) is 10wt.%; hollow glass bead/MnO 2 The preparation method comprises the following specific steps:
(1) Coarsening hollow glass beads with 5g/L KF solution and 5g/L SnC1 2 +5Sensitization of ml/L hydrochloric acid solution and 1g/LAgNO 3 Carrying out solution activation treatment to obtain activated hollow glass microspheres;
(2) The activated hollow glass beads were placed at a concentration of 10wt.% Mn (NO 3 ) 2 Soaking in absolute ethanol solution for 5min, and sintering at 100deg.C for 10min; repeatedly soaking and sintering for 4 times to obtain active hollow glass microsphere/MnO 2 ；
The modified carbon material composite powder is coconut shell active carbon chemical plating lead-tin alloy, wherein the lead content in the coconut shell active carbon chemical plating lead-tin alloy is 10wt.%, and the tin content is 10wt.%;
The preparation method of the coconut shell active carbon chemical plating lead-tin alloy comprises the following specific steps:
(1) Coarsening coconut shell activated carbon sequentially with 5g/L KF solution and 5g/L SnC1 2 +5ml/L hydrochloric acid solution sensitization, 0.2g/L PdC1 2 Carrying out solution activation treatment to obtain activated coconut shell activated carbon;
(2) Placing activated coconut shell activated carbon into neutral chemical plating lead-tin alloy liquid, and performing chemical plating at the temperature of 60 ℃ for 1h to obtain the coconut shell activated carbon chemical plating lead-tin alloy; the neutral electroless lead-tin alloy plating solution contains PbCl 2 10g/L，SnCl 2 10g/L EDTA 10g/L, trisodium citrate 60g/L, nitrilotriacetic acid 10g/L, tiCl 3 (50%) 10mL/L; the pH value of the neutral electroless lead-tin alloy plating liquid is 5;
the preparation method of the aluminum-based composite polar plate for the high-capacity long-life lead-carbon energy storage battery comprises the following specific steps:
s1, preparation of positive grid
Preparation of Ni-Sn/rare earth composite transition layer: sequentially carrying out alkali washing, deionized water washing, ultrasonic washing, primary zinc dipping, deionized water washing, nitric acid activation, deionized water washing, secondary zinc dipping, chemical composite plating Ni-Sn/rare earth, deionized water washing and drying on an aluminum alloy rod (1060) to obtain a Ni-Sn/rare earth composite transition layer composite rod;
the zinc leaching solution contains 200g/L of NaOH, 50g/L of ZnO, 5g/L of potassium sodium tartrate, and the zinc leaching temperature is 20 ℃ and the time is 30S;
The chemical composite plating Ni-Sn-The plating solution of rare earth contains NiSO 4 ·7H 2 O 25g/L，SnC1 4 5g/L，NaHPO 2 10g/L of sodium acetate 10g/L, 1ml/L of glacial acetic acid 1g/L of rare earth, the pH value of the plating solution is 4.4, the temperature of the chemical composite plating Ni-Sn/rare earth is 80 ℃, and the traction speed is 2m/min;
b. preparing a lead-calcium tin-aluminum interlayer: placing the Ni-Sn/rare earth composite transition layer composite rod in a drawing coating extruder, and coating semi-molten lead-calcium-tin-aluminum alloy on the surface of the Ni-Sn/rare earth composite transition layer composite rod to obtain an aluminum-based/lead-calcium-tin-aluminum composite rod;
c. bending the aluminum-based/lead-calcium-tin-aluminum composite rod to form a positive grid frame and positive symmetric S-shaped plate grid ribs, and welding the positive grid frame and the positive symmetric S-shaped plate grid ribs to form a grid-shaped positive plate; the specific method comprises the following steps: after the aluminum base/lead calcium tin aluminum composite rod is calibrated, the calibration point is taken as an arc vertex, the aluminum base/lead calcium tin aluminum composite rod is bent twice according to R=20mm to form a positive grid frame, and right angles are formed between the straight rods at the two ends of the arc; bending according to R=8mm, bending alternately in forward and reverse directions on a two-dimensional plane by taking a calibration point as an arc according to the calibration length of 20mm of the bending point spacing of the aluminum-based/lead-calcium-tin-aluminum composite rod, wherein the included angle between straight rods at two ends of the arc is 105 degrees, and the contact position between the bending rod and the bottom of the frame is set into an arc with radius R=10mm by taking the calibration point as the arc vertex according to the calibration length of 50mm of the bending point spacing;
d. Welding positive aluminum alloy conductive beam on top of grid type positive plate, placing in methylsulfonic acid solution A, taking cast pure lead plate as anode, and at 30deg.C, current density is 0.5A/dm 2 Electroplating a lead-cobalt-antimony rare earth/silver coated aluminum powder composite layer for 1h under mechanical stirring to obtain a positive grid; the methylsulfonic acid solution A contains lead methylsulfonate (Pb (CH) 3 SO 3 ) 2 ) 80g/L, cobalt methylsulfonate (Co (CH) 3 SO 3 ) 2 ) 8g/L, 4g/L of potassium antimonate tartrate and nano CeO 2 4g/L, silver Bao Lvfen g/L;
e. coating the positive lead plaster on a positive grid, and curing and drying to obtain a positive composite polar plate of the lead-carbon energy storage battery;
s2, preparation of negative grid
a.Ni-TiB 2 Preparation of a composite transition layer: sequentially performing alkaline washing, deionized water washing, ultrasonic washing, primary zinc leaching, deionized water washing, nitric acid activation, deionized water washing, secondary zinc leaching and chemical composite plating of Ni-TiB on aluminum or aluminum alloy 2 Washing with deionized water and drying to obtain Ni-TiB 2 A composite transition layer composite rod;
the zinc leaching solution contains 200g/L of NaOH, 50g/L of ZnO, 5g/L of potassium sodium tartrate, and the zinc leaching temperature is 20 ℃ and the time is 30S;
chemical composite plating Ni-TiB 2 The plating solution of (C) contains NiSO 4 ·7H 2 O40 g/L, hydrazine hydrate 10g/L, sodium acetate 10g/L, nano TiB 2 2g/L, pH value of plating solution is 9, and Ni-TiB is plated by chemical combination 2 The temperature of (2) is 80 ℃, and the traction speed is 2m/min;
b. preparing a lead-calcium-aluminum interlayer: ni-TiB 2 The composite transition layer composite rod is placed in a drawing cladding extruder for heat treatment for 5min at 120 ℃, and the semi-molten lead-calcium aluminum alloy is clad on Ni-TiB 2 The surface of the composite rod of the composite transition layer is provided with an aluminum-based/lead-calcium-aluminum composite rod;
c. bending the aluminum-based/lead-calcium-aluminum composite rod to form a negative grid frame and negative symmetrical S-shaped plate grid ribs, and welding the negative grid frame and the negative symmetrical S-shaped plate grid ribs to form a grid-type negative plate; the specific method comprises the following steps: after the aluminum-based/lead-calcium-aluminum composite rod is calibrated, the calibration point is taken as an arc vertex, the aluminum-based/lead-calcium-aluminum composite rod is bent twice according to R=20mm to form a negative grid frame, and right angles are formed between straight rods at two ends of the arc; according to the standard length of 20mm of the bending point spacing of the aluminum-based/lead-calcium-aluminum composite rod, bending according to R=8mm is laid on a two-dimensional plane by taking the standard point as an arc, bending alternately in forward and reverse directions, wherein the included angle between straight rods at two ends of the arc is 105 degrees, the contact position between the bending rod and the bottom of the frame is set into an arc with radius R=10mm by taking the standard point as the arc vertex according to the standard length of 50mm of the bending point spacing;
d. welding a negative aluminum alloy conductive beam on the top end of a grid-type negative plate, placing the negative aluminum alloy conductive beam in methylsulfonic acid liquid B, taking an as-cast pure lead plate as an anode, and controlling the current density to be 0.5A/dm at the temperature of 30 DEG C 2 Electroplating the lead tin antimony/zirconium dioxide composite layer for 1h under the condition of mechanical stirring to obtainTo the negative grid; the methylsulfonic acid solution B contains lead methylsulfonate (Pb (CH) 3 SO 3 ) 2 ) 40g/L, stannous methanesulfonate (Sn (CH) 3 SO 3 ) 2 ) 10g/L, 2g/L of potassium antimonate tartrate and nano ZrO 2 4g/L, o-chlorobenzaldehyde 0.1g/L;
e. coating negative lead plaster on a negative grid, and solidifying and drying to obtain a negative composite polar plate of the lead-carbon energy storage battery;
the battery assembly process comprises the following steps: the positive plate and the negative plate are both coated with separator paper on both sides, the negative electrode is a first sheet, then the positive electrode and the negative electrode are alternately laminated, the electrode group is of a 7 positive 8 negative structure, and the electrode group is clamped and pressed into the battery case; the battery is assembled after the sealing cover, the sealing and the air tightness detection, and finally the performance is tested;
the positive and negative plates manufactured by the composite grid of the embodiment have strong deformation resistance and creep resistance, and compared with the traditional lead-0.06% calcium-1.2% tin alloy grid, the tensile strength is improved by 50%, the plate conductivity is improved by 30%, the high-current discharge performance is improved by 10%, and the heavy metal lead consumption is reduced by 40%.
Example 3: the aluminum-based composite polar plate for the high-capacity long-service-life lead carbon energy storage battery of the embodiment is basically the same as the grid structure of the aluminum-based composite polar plate of the embodiment 1, and is different in that:
The aluminum-based lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite rod 11 sequentially comprises an aluminum alloy rod (1070), a Ni-Sn/rare earth composite transition layer, a lead-calcium-tin-aluminum intermediate layer and a lead-cobalt-antimony-rare earth/silver-coated aluminum powder active layer from inside to outside, and the aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod 21 sequentially comprises an aluminum alloy rod (6061) and Ni-TiB from inside to outside 2 The composite transition layer, the lead-calcium-aluminum intermediate layer and the lead-tin-antimony/zirconium dioxide particle outer layer; the section of the aluminum alloy rod (1070) in the aluminum-based lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite rod 11 is rectangular, the tooth depth is 0.3mm, the tooth width is 0.3mm, the diameter of the aluminum alloy rod (1070) is 6.0mm, the thickness of the Ni-Sn/rare earth composite transition layer is 10 mu m, the thickness of the lead-calcium-tin-aluminum intermediate layer is 6.0mm, and the thickness of the lead-cobalt-antimony-rare earth/silver-coated aluminum powder active layer is 1.0mm; the section of the aluminum alloy rod (6061) in the aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod 21 is rectangular, the tooth depth is 0.2mm, the tooth width is 0.2mm, and the aluminum alloy isThe diameter of the rod (6061) is 4.0mm, and the Ni-TiB 2 The thickness of the composite transition layer is 10 mu m, the thickness of the lead-calcium-aluminum intermediate layer is 4.0mm, and the thickness of the lead-tin-antimony/zirconium dioxide outer layer is 0.5mm;
the rare earth of the Ni-Sn/rare earth composite transition layer in the aluminum-based lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite rod 11 is Nd 2 O 3 The rare earth doping amount is 0.5wt.%; the lead-calcium-tin-aluminum interlayer has a calcium content of 0.1wt.%, a tin content of 0.6wt.%, and an aluminum content of 0.05wt.%; the rare earth in the lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer is La, the cobalt content is 0.2 wt%, the antimony content is 0.5 wt%, the rare earth content is 0.2 wt%, the silver-coated aluminum powder content is 2.0 wt%, and the silver content of the silver-coated aluminum powder is 25 wt%;
Ni-TiB in aluminum-based lead tin antimony/zirconium dioxide particle composite rod 21 2 TiB of composite transition layer 2 The doping amount is 1.0wt.%, the calcium content in the lead-calcium-aluminum intermediate layer is 0.12wt.%, the aluminum content is 0.1wt.%, and the rest is lead; the tin content in the lead tin antimony/zirconium dioxide outer layer is 2.0wt.%, the antimony content is 1wt.%, and the zirconium dioxide content is 5wt.%;
the grid-type positive plate comprises a positive grid frame and positive symmetrical S-shaped plate grid ribs, and the grid-type negative plate comprises a negative grid frame and negative symmetrical S-shaped plate grid ribs;
the thickness of the anode aluminum alloy conductive beam is 20mm, the thickness of the cathode aluminum alloy conductive beam is 18mm, and the anode aluminum alloy conductive beam and the cathode aluminum alloy conductive beam sequentially comprise aluminum or an aluminum alloy matrix, a hard anodic oxidation film layer, an anti-corrosion PTFE composite modified primer layer and a silica gel metal glue anti-corrosion layer from inside to outside;
The thickness of the hard anodic oxidation film layer is 50 mu m, the thickness of the anti-corrosion PTFE composite modified primer layer is 100 mu m, and the thickness of the anti-corrosion layer of the silica gel adhesive metal glue is 100 mu m;
the preparation method of the positive plate aluminum alloy conductive beam comprises the following specific steps:
(1) Sequentially carrying out alkali washing and oil removal and deionized water washing on the aluminum alloy conductive beam by using a NaOH solution with the concentration of 20wt.% to obtain a pretreated aluminum alloy conductive beam;
(2) Placing the pretreated aluminum alloy conductive beamIn modified sulfuric acid solution, the temperature is 5 ℃ and the current density is 4A/dm 2 Carrying out hard anodic oxidation for 4 hours under the condition of 50V tank voltage and bottom blowing stirring, cleaning by deionized water, sealing in hot water, blow-drying, and carrying out vacuum heat treatment for 2 hours at 600 ℃ to obtain a hard anodic oxidation film layer; the modified sulfuric acid solution contains 300g/L sulfuric acid, 30ml/L glycerin, 30g/L oxalic acid and 30g/L aluminum sulfate;
(3) Immersing the aluminum alloy conductive beam coated with the hard anodic oxidation film layer into modified PTFE emulsion with the temperature of 120 ℃ for coating for 10min to obtain an anti-corrosion PTFE composite modified primer layer;
(4) Coating commercial silica gel adhesive metal glue on the surface of an aluminum alloy conductive beam coated with an anti-corrosion PTFE composite modified primer layer at 120 ℃ and curing for 3 hours to obtain a silica gel adhesive metal glue anti-corrosion layer;
90% of lead powder and 90% of hollow glass beads/MnO (mass of the positive electrode lead paste) based on 100% 2 4.0%, tetrabasic lead sulphate powder 2.0%, colloidal graphite 0.8%, short fiber 0.20%, silicon dioxide 1.5%, sulfuric acid solution 11.5%, H 2 O13.0%; based on 100% of the mass of the negative electrode lead plaster, 85% of lead powder, 1.0% of colloidal graphite, 5.0% of modified carbon material composite powder, 1.0% of superfine barium sulfate, 0.5% of lignin, 0.20% of short fiber, 9.0% of sulfuric acid solution and H 2 O14%; the thickness of the positive electrode lead plaster layer is 9mm, and the thickness of the negative electrode lead plaster layer is 7mm;
hollow glass bead/MnO 2 Middle MnO 2 The content of (2) is 20wt.%; hollow glass bead/MnO 2 The preparation method comprises the following specific steps:
(1) Sequentially passing the hollow glass beads through 20g/L KF coarsening solution and 20g/L SnC1 2 Sensitization of +10ml/L hydrochloric acid solution, 5g/L AgNO 3 Carrying out solution activation treatment to obtain activated hollow glass microspheres;
(2) The activated hollow glass beads were placed in a concentration of 30wt.% Mn (NO 3 ) 2 Soaking in absolute ethanol solution for 20min, and sintering at 400 ℃ for 30min; repeatedly soaking and sintering for 8 times to obtain active hollow glass microsphere/MnO 2 ；
The modified carbon material composite powder is coconut shell active carbon chemical plating lead-tin alloy, wherein the lead content in the coconut shell active carbon chemical plating lead-tin alloy is 10wt.%, and the tin content is 10wt.%;
The preparation method of the coconut shell active carbon chemical plating lead-tin alloy comprises the following specific steps:
(1) Coarsening coconut shell activated carbon sequentially with 20g/L KF solution and 20g/L SnC1 2 +10ml/L hydrochloric acid solution sensitization, 1.0g/L PdCl 2 Carrying out solution activation treatment to obtain activated coconut shell activated carbon;
(2) Placing activated coconut shell activated carbon into neutral chemical plating lead-tin alloy liquid, and performing chemical plating for 3 hours at the temperature of 80 ℃ to obtain the coconut shell activated carbon chemical plating lead-tin alloy; the neutral electroless lead-tin alloy plating liquid contains PbC1 2 30g/L，SnC1 2 30g/L, EDTA 40g/L, trisodium citrate 100g/L, nitrilotriacetic acid 40g/L, tiC1 3 (50%) 40mL/L; the pH value of the neutral electroless lead-tin alloy plating liquid is 8;
the preparation method of the aluminum-based composite polar plate for the high-capacity long-life lead-carbon energy storage battery comprises the following specific steps:
s1, preparation of positive grid
Preparation of Ni-Sn/rare earth composite transition layer: sequentially carrying out alkali washing, deionized water washing, ultrasonic washing, primary zinc dipping, deionized water washing, nitric acid activation, deionized water washing, secondary zinc dipping, chemical composite plating Ni-Sn/rare earth, deionized water washing and drying on an aluminum alloy rod (1070) to obtain a Ni-Sn/rare earth composite transition layer composite rod;
the zinc leaching solution contains 400g/L of NaOH, 100g/L of ZnO, 20g/L of potassium sodium tartrate, and the zinc leaching temperature is 40 ℃ and the time is 100S;
The plating solution for chemically plating Ni-Sn/rare earth contains NiSO 4 ·7H 2 O 45g/L，SnC1 4 15g/L，NaHPO 2 30g/L of sodium acetate 30g/L, 10ml/L of glacial acetic acid 10g/L of rare earth, pH value of plating solution of 5.0, temperature of chemical composite plating Ni-Sn/rare earth of 95 ℃ and traction speed of 8m/min;
b. preparing a lead-calcium tin-aluminum interlayer: placing the Ni-Sn/rare earth composite transition layer composite rod in a drawing coating extruder, and coating semi-molten lead-calcium-tin-aluminum alloy on the surface of the Ni-Sn/rare earth composite transition layer composite rod to obtain an aluminum-based/lead-calcium-tin-aluminum composite rod;
c. bending the aluminum-based/lead-calcium-tin-aluminum composite rod to form a positive grid frame and positive symmetric S-shaped plate grid ribs, and welding the positive grid frame and the positive symmetric S-shaped plate grid ribs to form a grid-shaped positive plate; the specific method comprises the following steps: after the aluminum base/lead calcium tin aluminum composite rod is calibrated, the calibration point is taken as an arc vertex, the aluminum base/lead calcium tin aluminum composite rod is bent twice according to R=30mm to form a positive grid frame, and right angles are formed between the straight rods at the two ends of the arc; bending according to R=30mm, bending alternately in forward and reverse directions on a two-dimensional plane by taking a calibration point as an arc according to the 60mm calibration length of the bending point spacing of the aluminum-based/lead-calcium-tin-aluminum composite rod, wherein the included angle between straight rods at two ends of the arc is 130 degrees, and the contact position between the bending rod and the bottom of the frame is set into an arc with radius R=40mm by taking the calibration point as the arc vertex according to the 80mm calibration length of the bending point spacing;
d. Welding a positive aluminum alloy conductive beam on the top end of a grid-type positive plate, placing the positive aluminum alloy conductive beam in methylsulfonic acid liquid A, taking an as-cast pure lead plate as an anode, and controlling the current density to be 4.0A/dm at the temperature of 60 DEG C 2 Electroplating a lead-cobalt-antimony rare earth/silver coated aluminum powder composite layer for 6 hours under mechanical stirring to obtain a positive grid; the methylsulfonic acid solution A contains lead methylsulfonate (Pb (CH) 3 SO 3 ) 2 ) 200g/L, cobalt methylsulfonate (Co (CH) 3 SO 3 ) 2 ) 24g/L, 12g/L of potassium antimonate tartrate and nano CeO 2 20g/L, bao Lvfen g/L of silver;
e. coating the positive lead plaster on a positive grid, and curing and drying to obtain a positive composite polar plate of the lead-carbon energy storage battery;
s2, preparation of negative grid
a.Ni-TiB 2 Preparation of a composite transition layer: sequentially performing alkaline washing, deionized water washing, ultrasonic washing, primary zinc leaching, deionized water washing, nitric acid activation, deionized water washing, secondary zinc leaching and chemical composite plating of Ni-TiB on aluminum or aluminum alloy 2 Washing with deionized water and drying to obtain Ni-TiB 2 A composite transition layer composite rod;
the zinc leaching solution contains 400g/L of NaOH, 100g/L of ZnO, 20g/L of potassium sodium tartrate, and the zinc leaching temperature is 40 ℃ and the time is 100S;
chemical composite plating Ni-TiB 2 The plating solution of (C) contains NiSO 4 ·7H 2 O100 g/L, hydrazine hydrate 30g/L, sodium acetate 30g/L, nano TiB 2 12g/L, pH value of plating solution is 10, and Ni-TiB is plated by chemical combination 2 The temperature of (2) is 95 ℃, and the traction speed is 8m/min;
b. preparing a lead-calcium-aluminum interlayer: ni-TiB 2 The composite transition layer composite rod is placed in a drawing cladding extruder for heat treatment for 10min at 300 ℃, and the semi-molten lead-calcium aluminum alloy is clad on Ni-TiB 2 The surface of the composite rod of the composite transition layer is provided with an aluminum-based/lead-calcium-aluminum composite rod;
c. bending the aluminum-based/lead-calcium-aluminum composite rod to form a negative grid frame and negative symmetrical S-shaped plate grid ribs, and welding the negative grid frame and the negative symmetrical S-shaped plate grid ribs to form a grid-type negative plate; the specific method comprises the following steps: after the aluminum-based/lead-calcium-aluminum composite rod is calibrated, the calibration point is taken as an arc vertex, the aluminum-based/lead-calcium-aluminum composite rod is bent twice according to R=30mm to form a negative grid frame, and right angles are formed between straight rods at two ends of the arc; according to the standard length of 60mm of the bending point spacing of the aluminum-based/lead-calcium-aluminum composite rod, bending according to R=30mm is laid on a two-dimensional plane by taking the standard point as an arc, bending alternately in forward and reverse directions, wherein the included angle between straight rods at two ends of the arc is 130 degrees, the contact position between the bending rod and the bottom of the frame is set into an arc with radius R=40mm by taking the standard point as the arc vertex according to the standard length of 80mm of the bending point spacing;
d. welding a negative aluminum alloy conductive beam on the top end of a grid-type negative plate, placing the negative aluminum alloy conductive beam in methylsulfonic acid liquid B, taking an as-cast pure lead plate as an anode, and controlling the current density to be 4.0A/dm at the temperature of 60 DEG C 2 Electroplating the lead-tin-antimony/zirconium dioxide composite layer for 6 hours under the condition of mechanical stirring to obtain a negative grid; the methylsulfonic acid solution B contains lead methylsulfonate (Pb (CH) 3 SO 3 ) 2 ) 120g/L, stannous methanesulfonate (Sn (CH) 3 SO 3 ) 2 ) 30g/L, 8g/L of potassium antimonate tartrate and nano ZrO 2 20g/L o-chlorobenzaldehyde 0.5g/L;
e. coating negative lead plaster on a negative grid, and solidifying and drying to obtain a negative composite polar plate of the lead-carbon energy storage battery;
the battery assembly process comprises the following steps: the positive plate and the negative plate are both coated with separator paper on both sides, the negative electrode is a first sheet, then the positive electrode and the negative electrode are alternately laminated, the electrode group is of a 7 positive 8 negative structure, and the electrode group is clamped and pressed into the battery case; the battery is assembled after the sealing cover, the sealing and the air tightness detection, and finally the performance is tested;
the positive and negative plates manufactured by the composite grid of the embodiment have strong deformation resistance and creep resistance, compared with the traditional lead-0.06% calcium-1.2% tin alloy grid, the tensile strength is improved by 60%, the plate conductivity is improved by 35%, the high-current discharge performance is improved by 20%, and the heavy metal lead consumption is reduced by 45%.
While the specific embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. An aluminum-based composite polar plate for a high-capacity long-life lead-carbon energy storage battery is characterized in that: the lead-carbon energy storage battery positive composite polar plate comprises a positive polar plate (1) and positive lead plaster coated on the positive polar plate (1), and the lead-carbon energy storage battery negative composite polar plate comprises a negative polar plate (2) and negative lead plaster coated on the negative polar plate (2);
the positive grid (1) comprises a grid type positive plate and a positive plate aluminum conductive beam (12) arranged at the top end of the grid type positive plate, and the negative grid (2) comprises a grid type negative plate and a negative plate aluminum conductive beam (22) arranged at the top end of the grid type negative plate; the grid-type positive plate consists of an aluminum-based lead-cobalt-antimony rare earth/silver coated aluminum powder composite rod (11), and the grid-type negative plate consists of an aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod (21);
positive plate aluminum conductive beam (12) top is fixed to be provided with anodal ear (13), and the top of negative pole aluminum conductive beam is fixed to be provided with negative pole ear (23), and anodal ear (13) are connected through positive L type aluminium bar that converges, and negative pole ear (23) are connected through negative L type aluminium bar that converges, and positive L type aluminium bar that converges and negative L type aluminium bar's end all is provided with the copper aluminium composite conductor head of external power cord.
The aluminum-based lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite rod (11) sequentially comprises an aluminum or aluminum alloy rod, a Ni-Sn/rare earth composite transition layer, a lead-calcium-tin-aluminum intermediate layer and a lead-cobalt-antimony-rare earth/silver-coated aluminum powder active layer from inside to outside, and the aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod (21) sequentially comprises an aluminum or aluminum alloy rod and Ni-TiB from inside to outside 2 A composite transition layer, a lead-calcium-aluminum intermediate layer and a lead-tin-antimony/zirconium dioxide particle outer layer.
2. The aluminum-based composite pole plate for the high-capacity long-life lead-carbon energy storage battery of claim 1, wherein the aluminum-based composite pole plate is characterized in that: the section of the aluminum or aluminum alloy rod in the aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod (11) is rectangular, the tooth depth is 0.1-0.3 mm, the tooth width is 0.05-0.3 mm, the diameter of the aluminum or aluminum alloy rod is 0.5-6.0 mm, the thickness of the Ni-Sn/rare earth composite transition layer is 1-10 mu m, the thickness of the lead-calcium-tin-aluminum intermediate layer is 0.5-6.0 mm, and the thickness of the lead-cobalt-antimony rare earth/silver-coated aluminum powder active layer is 0.1-1.0 mm; the section of the aluminum or aluminum alloy rod in the aluminum-based lead-tin-antimony/zirconium dioxide particle composite rod (21) is rectangular, the tooth depth is 0.05-0.2 mm, the tooth width is 0.05-0.2 mm, the diameter of the aluminum or aluminum alloy rod is 0.5-4.0 mm, and the Ni-TiB 2 The thickness of the composite transition layer is 1-10 mu m, the thickness of the lead-calcium-aluminum intermediate layer is 0.5-4.0 mm, and the thickness of the lead-tin-antimony/zirconium dioxide outer layer is 0.1-0.5 mm.
3. The aluminum-based composite pole plate for the high-capacity long-life lead-carbon energy storage battery of claim 1, wherein the aluminum-based composite pole plate is characterized in that: the rare earth of the Ni-Sn/rare earth composite transition layer in the aluminum-based lead-cobalt-antimony rare earth/silver-coated aluminum powder composite rod (11) is CeO 2 、La 2 O 3 Or Nd 2 O 3 The doping amount of rare earth is 0.05 to 0.5wt percent; the content of calcium in the lead-calcium tin-aluminum interlayer is 0.04 to 0.1wt percent, the content of tin is 0.1 to 0.6wt percent, and the content of aluminum is 0.01 to 0.05wt percent; the rare earth in the active layer of the Pb-Co-Sb rare earth/silver-coated aluminum powder is Ce, nd, pr or La, the cobalt content is 0.01 to 0.2wt percent, the antimony content is 0.05 to 0.5wt percent, and the rare earth content is 0.01 to 0.2wt percentThe content of the silver-coated aluminum powder is 0.2 to 2wt percent, and the content of the silver-coated aluminum powder is 5 to 25wt percent;
Ni-TiB in aluminum-based lead tin antimony/zirconium dioxide particle composite rod (21) 2 TiB of composite transition layer 2 The doping amount is 0.1-1 wt%, the calcium content in the lead-calcium-aluminum intermediate layer is 0.05-0.12 wt%, the aluminum content is 0.01-0.1 wt%, and the rest is lead; the tin content in the lead tin antimony/zirconium dioxide outer layer is 0.5-2.0 wt%, the antimony content is 0.1-1 wt%, and the zirconium dioxide content is 0.5-5 wt%.
4. The aluminum-based composite pole plate for the high-capacity long-life lead-carbon energy storage battery of claim 1, wherein the aluminum-based composite pole plate is characterized in that: the grid type positive plate comprises a positive grid frame and positive symmetrical S-shaped plate grid ribs, and the grid type negative plate comprises a negative grid frame and negative symmetrical S-shaped plate grid ribs.
5. The aluminum-based composite pole plate for the high-capacity long-life lead-carbon energy storage battery of claim 1, wherein the aluminum-based composite pole plate is characterized in that: the positive plate aluminum conductive beam (12) and the negative plate aluminum conductive beam (22) sequentially comprise an aluminum or aluminum alloy matrix, a hard anodic oxidation film layer, an anti-corrosion PTFE composite modified primer layer and a silica gel adhesive metal glue anti-corrosion layer from inside to outside.
6. The aluminum-based composite pole plate for the high-capacity long-life lead-carbon energy storage battery as claimed in claim 5, wherein the aluminum-based composite pole plate is characterized in that: the thickness of the hard anodic oxidation film layer is 20-50 mu m, the thickness of the anti-corrosion PTFE composite modified primer layer is 20-100 mu m, and the thickness of the anti-corrosion layer of the silica gel adhesive metal glue is 40-200 mu m.
7. The aluminum-based composite pole plate for the high-capacity long-life lead-carbon energy storage battery of claim 1, wherein the aluminum-based composite pole plate is characterized in that: 75-90% of lead powder and 75-90% of hollow glass bead/MnO (mass of positive electrode lead paste) based on 100% of positive electrode lead paste 2 1.0 to 4.0 percent, tetrabasic lead sulfate powder 1.0 to 2.0 percent, colloidal graphite 0.1 to 0.8 percent, short fiber 0.1 to 0.2 percent, silicon dioxide 0.5 to 1.5 percent, sulfuric acid solution 6.0 to 11.5 percent and H 2 9.0 to 13.0 percent of O; takes the mass of the negative electrode lead plaster as100 percent of lead powder 75 to 85 percent, colloid graphite 0.2 to 1.0 percent, modified carbon material composite powder 0.5 to 5.0 percent, superfine barium sulfate 0.3 to 1.0 percent, lignin 0.1 to 0.5 percent, short fiber 0.1 to 0.2 percent, sulfuric acid solution 6.0 to 9.0 percent and H 2 9-14% of O; the thickness of the positive electrode lead plaster layer is 5-9 mm, and the thickness of the negative electrode lead plaster layer is 4-7 mm.
8. The aluminum-based composite pole plate for the high-capacity long-life lead-carbon energy storage battery of claim 7, wherein the aluminum-based composite pole plate is characterized in that: hollow glass bead/MnO 2 Middle MnO 2 The content of (2) is 10-20 wt.%;
the modified carbon material composite powder is coconut shell active carbon chemical plating lead-tin alloy, wherein the lead content in the coconut shell active carbon chemical plating lead-tin alloy is 10-20 wt.%, and the tin content is 10-20 wt.%.
9. The method for preparing the aluminum-based composite polar plate for the high-capacity long-service-life lead-carbon energy storage battery as claimed in any one of claims 1 to 8, which is characterized by comprising the following specific steps:
s1, preparation of positive grid
Preparation of Ni-Sn/rare earth composite transition layer: sequentially carrying out alkali washing, deionized water washing, ultrasonic washing, primary zinc leaching, deionized water washing, nitric acid activation, deionized water washing, secondary zinc leaching, chemical composite plating of Ni-Sn/rare earth, deionized water washing and drying on aluminum or aluminum alloy to obtain a Ni-Sn/rare earth composite transition layer composite rod;
b. preparing a lead-calcium tin-aluminum interlayer: placing the Ni-Sn/rare earth composite transition layer composite rod in a drawing coating extruder, and coating semi-molten lead-calcium-tin-aluminum alloy on the surface of the Ni-Sn/rare earth composite transition layer composite rod to obtain an aluminum-based/lead-calcium-tin-aluminum composite rod;
c. Bending the aluminum-based/lead-calcium-tin-aluminum composite rod to form a positive grid frame and positive symmetric S-shaped plate grid ribs, and welding the positive grid frame and the positive symmetric S-shaped plate grid ribs to form a grid-shaped positive plate;
d. welding a positive aluminum conductive beam on the top end of a grid type positive plate, and placing the positive aluminum conductive beam in methylsulfonic acid liquid A to electroplate a lead-cobalt-antimony-rare earth/silver-coated aluminum powder composite layer to obtain a positive grid;
e. coating the positive lead plaster on a positive grid, and curing and drying to obtain a positive composite polar plate of the lead-carbon energy storage battery;
s2, preparation of negative grid
a.Ni-TiB 2 Preparation of a composite transition layer: sequentially performing alkaline washing, deionized water washing, ultrasonic washing, primary zinc leaching, deionized water washing, nitric acid activation, deionized water washing, secondary zinc leaching and chemical composite plating of Ni-TiB on aluminum or aluminum alloy 2 Washing with deionized water and drying to obtain Ni-TiB 2 A composite transition layer composite rod;
b. preparing a lead-calcium-aluminum interlayer: ni-TiB 2 The composite transition layer composite rod is placed in a drawing coating extruder for heat treatment for 5 to 10 minutes at the temperature of 120 to 300 ℃ and is coated with semi-molten lead-calcium aluminum alloy in Ni-TiB 2 The surface of the composite rod of the composite transition layer is provided with an aluminum-based/lead-calcium-aluminum composite rod;
c. bending the aluminum-based/lead-calcium-aluminum composite rod to form a negative grid frame and negative symmetrical S-shaped plate grid ribs, and welding the negative grid frame and the negative symmetrical S-shaped plate grid ribs to form a grid-type negative plate;
d. Welding a negative aluminum conductive beam on the top end of a grid-type negative plate, and placing the negative aluminum conductive beam in methylsulfonic acid liquid B to electroplate a lead-tin-antimony/zirconium dioxide composite layer to obtain a negative grid;
e. and (3) coating the negative electrode lead plaster on a negative electrode grid, and curing and drying to obtain the negative electrode composite polar plate of the lead-carbon energy storage battery.
10. The method for preparing the aluminum-based composite polar plate for the high-capacity long-service-life lead-carbon energy storage battery, which is characterized by comprising the following steps of:
the zinc dipping liquid contains 200-400 g/L of NaOH, 50-100 g/L of ZnO, 5-20 g/L of potassium sodium tartrate, and the zinc dipping temperature is 20-40 ℃ and the time is 30-100S;
the plating solution for chemically plating Ni-Sn/rare earth contains NiSO 4 ·7H 2 O 25～45g/L，SnC1 4 5～15g/L，NaHPO 2 10 to 30g/L, 10 to 30g/L sodium acetate, 1 to 10ml/L glacial acetic acid and 1 to 10g/L rare earth, and platingThe pH value of the solution is 4.4-5.0, the temperature of the chemical composite plating Ni-Sn/rare earth is 80-95 ℃, and the traction speed is 2-8m/min;
the methylsulfonic acid liquid A contains 80-200 g/L of lead methylsulfonate, 8-24 g/L of cobalt methylsulfonate, 4-12 g/L of potassium antimony tartrate and nano CeO 2 4-20 g/L, and 2-10 g/L of silver-coated aluminum powder; the anode of the electroplated lead-cobalt-antimony rare earth/silver coated aluminum powder composite layer is an as-cast pure lead plate, the temperature is 30-60 ℃, and the current density is 0.5-4A/dm 2 The time is 1-6 h;
chemical composite plating Ni-TiB 2 The plating solution of (C) contains NiSO 4 ·7H 2 40-100 g/L of O, 10-30 g/L of hydrazine hydrate, 10-30 g/L of sodium acetate and nano TiB 2 2-12 g/L, pH value of plating solution is 9-10, and Ni-TiB is chemically plated 2 The temperature of the belt is 80-95 ℃ and the traction speed is 2-8 m/min;
the methylsulfonic acid liquid B contains 40-120 g/L of lead methylsulfonate, 10-30 g/L of stannous methylsulfonate, 2-8 g/L of potassium antimony tartrate and nano ZrO 2 4-20 g/L, 0.1-0.5 g/L o-chlorobenzaldehyde; the anode of the electroplated lead-tin-antimony/zirconium dioxide composite layer is an as-cast pure lead plate, the temperature is 30-60 ℃, and the current density is 0.5-4A/dm 2 The time is 1-6 h.
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| CN117790699B (en) * | 2024-02-23 | 2024-04-26 | 昆明理工恒达科技股份有限公司 | Full-automatic assembly equipment of aluminium base lead alloy composite electrode |
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