CN115807245A - Energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition and preparation method thereof - Google Patents
Energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition and preparation method thereof Download PDFInfo
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- CN115807245A CN115807245A CN202211647945.3A CN202211647945A CN115807245A CN 115807245 A CN115807245 A CN 115807245A CN 202211647945 A CN202211647945 A CN 202211647945A CN 115807245 A CN115807245 A CN 115807245A
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- aluminum
- composite
- lead
- layer
- anode plate
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- 239000002131 composite material Substances 0.000 title claims abstract description 241
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 36
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 188
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 182
- -1 aluminum-titanium-boron Chemical compound 0.000 claims abstract description 68
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 claims abstract description 65
- 239000010949 copper Substances 0.000 claims abstract description 65
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 47
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 39
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 claims abstract description 37
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 30
- 239000011701 zinc Substances 0.000 claims abstract description 30
- 230000007704 transition Effects 0.000 claims abstract description 28
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 24
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 16
- 239000010410 layer Substances 0.000 claims description 139
- 238000007747 plating Methods 0.000 claims description 77
- 238000005406 washing Methods 0.000 claims description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 239000008367 deionised water Substances 0.000 claims description 54
- 229910021641 deionized water Inorganic materials 0.000 claims description 54
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 41
- 239000003365 glass fiber Substances 0.000 claims description 36
- 229910052709 silver Inorganic materials 0.000 claims description 34
- 239000004332 silver Substances 0.000 claims description 34
- 239000004744 fabric Substances 0.000 claims description 33
- 239000000110 cooling liquid Substances 0.000 claims description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 26
- 230000004913 activation Effects 0.000 claims description 26
- 229910052718 tin Inorganic materials 0.000 claims description 26
- 238000001125 extrusion Methods 0.000 claims description 22
- 239000011246 composite particle Substances 0.000 claims description 21
- 150000002910 rare earth metals Chemical class 0.000 claims description 20
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 14
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 14
- 235000011180 diphosphates Nutrition 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052797 bismuth Inorganic materials 0.000 claims description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 12
- 238000005253 cladding Methods 0.000 claims description 12
- 239000002344 surface layer Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 238000003466 welding Methods 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000004512 die casting Methods 0.000 claims description 9
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 claims description 8
- 239000012212 insulator Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims 1
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 43
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- 239000011159 matrix material Substances 0.000 description 21
- 229910001128 Sn alloy Inorganic materials 0.000 description 20
- 238000009713 electroplating Methods 0.000 description 20
- 230000003213 activating effect Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 229910001245 Sb alloy Inorganic materials 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 13
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 13
- 230000001235 sensitizing effect Effects 0.000 description 13
- 239000001119 stannous chloride Substances 0.000 description 13
- 235000011150 stannous chloride Nutrition 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 12
- 239000002140 antimony alloy Substances 0.000 description 12
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 12
- 229940079864 sodium stannate Drugs 0.000 description 12
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 11
- 229910000978 Pb alloy Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 238000009740 moulding (composite fabrication) Methods 0.000 description 8
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 8
- 238000005554 pickling Methods 0.000 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 description 8
- 230000008569 process Effects 0.000 description 8
- 230000002035 prolonged effect Effects 0.000 description 8
- 239000001509 sodium citrate Substances 0.000 description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 235000002906 tartaric acid Nutrition 0.000 description 7
- 239000011975 tartaric acid Substances 0.000 description 7
- 101150003085 Pdcl gene Proteins 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 230000003064 anti-oxidating effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 5
- 229940074439 potassium sodium tartrate Drugs 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- JALQQBGHJJURDQ-UHFFFAOYSA-L bis(methylsulfonyloxy)tin Chemical compound [Sn+2].CS([O-])(=O)=O.CS([O-])(=O)=O JALQQBGHJJURDQ-UHFFFAOYSA-L 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229940046892 lead acetate Drugs 0.000 description 4
- 229910000464 lead oxide Inorganic materials 0.000 description 4
- 229940098779 methanesulfonic acid Drugs 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 4
- 238000005488 sandblasting Methods 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229910001094 6061 aluminium alloy Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229940026189 antimony potassium tartrate Drugs 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000010288 cold spraying Methods 0.000 description 3
- 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 3
- 238000005363 electrowinning Methods 0.000 description 3
- 229910001325 element alloy Inorganic materials 0.000 description 3
- 238000007765 extrusion coating Methods 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QDMRQDKMCNPQQH-UHFFFAOYSA-N boranylidynetitanium Chemical compound [B].[Ti] QDMRQDKMCNPQQH-UHFFFAOYSA-N 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 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 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to an energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition and a preparation method thereof, belonging to the technical field of non-ferrous metallurgy. The composite anode plate comprises an aluminum conductive beam, wherein a copper-aluminum composite conductive head is fixedly arranged at the end of the aluminum conductive beam, a fence type aluminum-based composite anode plate support is fixedly arranged at the bottom end of the aluminum conductive beam, a plurality of layers of horizontal conductive reinforcing ribs are fixedly arranged on the fence type aluminum-based composite anode plate support along the longitudinal direction, two sides of the fence type aluminum-based composite anode plate support are coated with insulating sheaths, and two ends of each conductive reinforcing rib are arranged in the corresponding insulating sheath; the fence type aluminum-based composite anode plate support consists of a plurality of parallel anode composite rods, wherein each anode composite rod sequentially comprises an aluminum alloy rod, a transition layer, a lead-bismuth-antimony/rare earth-nano cobalt composite layer and an aluminum-titanium-boron particle surface coating lead-silver composite coating from inside to outside; wherein the transition layer comprises a zinc layer, a copper layer and a lead-tin-rare earth composite layer from inside to outside in sequence.
Description
Technical Field
The invention relates to an energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition and a preparation method thereof, belonging to the technical field of non-ferrous metallurgy.
Background
The insoluble anode materials currently used for extraction of nonferrous and rare metals are mainly lead-based alloys and titanium-based coated anodes. In the process of non-ferrous metal electrodeposition, the performance of the anode material directly influences the indexes such as ion discharge potential, overpotential change, current efficiency, electric energy consumption, anode service life, cathode product quality and the like. In the zinc, copper, nickel, manganese, cobalt and other nonferrous metal hydrometallurgical industries nationwide and even worldwide, lead alloy is used as an anode material for more than 100 years, but the lead alloy anode has the key technical problems of high oxygen evolution overpotential, low mechanical strength, lead dissolution, metal product pollution and the like and cannot be fundamentally solved. Although the titanium-based coating can solve the problems of the lead-based alloy anode, the quality of the electro-deposited zinc is improved.However, titanium-based PbO without intermediate layer 2 The anode is difficult to conduct because titanium is easy to passivate, and in addition, the price of titanium is high and the production cost is high. The use of titanium-based anodes with an intermediate layer, while improving the robustness, conductivity and corrosion resistance of the anode to some extent, further increases the cost and limits the large-scale use of the anode.
The composite anode is prepared by utilizing the light weight and excellent electric conductivity of aluminum and the excellent electrochemical performance of lead alloy, is light in weight relative to the lead alloy, receives wide attention, and is obtained by mutually dissolving light metal aluminum serving as an inner core and the outer lead alloy in a fusion casting or electroplating mode: the problems which are difficult to solve exist, namely, the fluidity of the lead alloy liquid and holes which may be formed on the part of the large-size anode plate cannot be solved; secondly, some grain boundary gaps can appear on the coating, and oxygen generated during electrolysis permeates the grain boundary gap alumina matrix of the coating to form an alumina film layer with poor conductivity, so that the performance of the anode is deteriorated.
The fence type anode plate for extracting metal by hydrometallurgy can improve the current density of the anode, improve the flowing property of electrolyte, improve the effect and quality of collecting electrolytic nonferrous metal, and avoid the defect that the anode plate is touched when the cathode plate is lifted. The cheap aluminum bar is adopted as a matrix, the material cost is obviously reduced, but the problems that the voltage of the groove is higher, the surface of the conductive beam is easy to crystallize and generate a short circuit phenomenon, the insulating sheath influences the distribution of a power line, the yield of a cathode product is reduced, the service life is short and the like still exist.
Disclosure of Invention
Aiming at the problems of the anode plate in the hydrometallurgy, the invention provides the energy-saving high-strength fence type composite anode plate for the non-ferrous metal electrodeposition and the preparation method thereof, the anode plate has high electrode strength, low cell voltage in the electrolytic process, long service life, less anode mud generated by the anode and high cathode product quality; according to the invention, the aging-resistant and corrosion-resistant glass fiber surface metalized lead alloy layer is introduced to coat the beam body, so that the crystallization of the conductive beam body is prevented, the heat dissipation performance is improved, the cooling liquid circulation channel is arranged in the conductive beam body, and the anti-oxidation water is introduced for circulating cooling, so that the heating problem of the beam is avoided; active silver nanoparticles are introduced to the working surface of the anode to coat the aluminum-titanium-boron composite particles with good conductivity and strong hardness, so that the electrocatalytic activity of the anode is improved and the service life of the anode is prolonged; compared with the traditional lead-silver multi-element alloy, on the basis of not changing the structure of an electrolytic cell, the composition of an electrolyte and the operation specification, the service life of the anode prepared by the method is prolonged by 1 time, the manganese dioxide particles coated on the surface of the electrode are few, the cell voltage is reduced by more than 10 percent, the current efficiency is improved by more than 3 percent, the quality of a cathode product is high, and the current density in the electrolytic process can be improved by 1 time.
An energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition comprises an aluminum conductive beam 1, wherein a copper-aluminum composite conductive head 2 is fixedly arranged at the end of the aluminum conductive beam 1, a fence type aluminum-based composite anode plate support 3 is fixedly arranged at the bottom end of the aluminum conductive beam 1, a plurality of layers of horizontal conductive reinforcing ribs 6 are fixedly arranged on the fence type aluminum-based composite anode plate support 3 along the longitudinal direction, insulating sheaths 4 are coated on two sides of the fence type aluminum-based composite anode plate support 3, and two ends of each conductive reinforcing rib 6 are arranged in the corresponding insulating sheath 4;
the fence type aluminum-based composite anode plate bracket 3 consists of a plurality of parallel anode composite rods 7, wherein each anode composite rod 7 sequentially comprises an aluminum alloy rod 71, a transition layer 72, a lead-bismuth-antimony/rare earth-nano cobalt composite layer 73 and an aluminum-titanium-boron particle surface coated lead-silver composite coating 74 from inside to outside; the transition layer 72 sequentially comprises a zinc layer, a copper layer and a lead-tin-rare earth composite layer from inside to outside.
The copper-aluminum composite conductive head 2 consists of an inner layer copper bar 22 and an aluminum cladding layer 21.
The aluminum conductive beam 1 sequentially comprises aluminum or aluminum alloy, glass fiber cloth and a lead-tin layer from inside to outside.
And a cooling liquid circulating channel parallel to the aluminum conductive beam 1 is formed in the aluminum conductive beam 1, and cooling liquid is filled in the cooling liquid circulating channel.
The height of the aluminum conductive beam 1 is 10-60 mm, the thickness is 10-40 mm, the thickness of the glass fiber cloth is 0.2-2 mm, the thickness of the lead-tin layer is 0.1-2 mm, and the diameter of the cooling liquid circulating channel is 0.5-10 mm.
The copper bar 22 of the inner layer in the copper-aluminum composite conductive head 2 is of an isomeric structure, and the thickness is 5-20 mm; the aluminum cladding layer 21 comprises a tin transition layer and an aluminum surface layer, wherein the thickness of the tin transition layer is 1-10 mu m, and the thickness of the aluminum surface layer is 5-30 mm.
The thickness of a zinc layer in the transition layer 72 is 0.5-2 mu m, the thickness of a copper layer is 3-8 mu m, and the thickness of a lead-tin rare earth composite layer is 4-20 mu m; the mass percentage of tin in the lead-tin-rare earth composite layer is 5-30%, the mass percentage of rare earth is 0.01-0.5%, and the balance is lead.
Based on the mass fraction of the lead bismuth antimony/rare earth-nano cobalt composite layer 73 as 100%, bismuth accounts for 0.01-1%, antimony accounts for 0.5-5%, rare earth accounts for 0.01-0.1%, nano cobalt accounts for 0.01-0.5%, and the balance is Pb.
In the lead-silver composite coating 74 coated on the surface of the aluminum-titanium-boron particles, the granularity of the aluminum-titanium-boron particles is 0.05-0.5 mm, and the thickness of the lead-silver composite coating is 0.1-0.6 mm; the lead accounts for 5-12%, the silver accounts for 0.5-3.0%, the titanium accounts for 1-5%, the boron accounts for 0.1-1% and the balance is aluminum, wherein the mass fraction of the lead-silver composite coating 74 coated on the surface of the aluminum-titanium-boron particles is 100%.
The conductive reinforcing rib 6 is a lead-tin-antimony alloy reinforcing rib, and the mass fraction of the lead-tin-antimony alloy is 100%, wherein the lead accounts for 88-98%, the tin accounts for 1-6%, and the antimony accounts for 1-6%.
Preferably, the width of the conductive reinforcing rib 6 is 10-100 mm, and the thickness is 6-20 mm.
The preparation method of the energy-saving high-strength fence type composite anode plate for the nonferrous metal electrodeposition comprises the following specific steps:
1) Sequentially carrying out alkali washing, deionized water washing, ultrasonic cleaning, acid activation treatment, deionized water washing, zinc dipping treatment, deionized water washing, pyrophosphate copper plating treatment, deionized water washing, methylsulfonate lead-tin rare earth alloy plating treatment, deionized water washing, lead-bismuth-antimony-rare earth nano cobalt powder plating treatment of a fluoboric acid system, deionized water washing, extrusion drawing composite rod treatment, acid washing for oil removal, deionized water washing and drying, spraying aluminum-titanium-boron composite particles with surfaces coated with lead and silver, carrying out heat treatment, taking up and carrying out fixed-length shearing on an aluminum wire to obtain an anode composite rod;
preferably, the alkaline washing solution contains 10100g/L NaOH and 5-20 g/L Na 2 CO 3 The alkali washing temperature is 50-70 ℃, and the alkali washing soaking time is 20-100 s;
preferably, the acid activation solution contains 20-50% of nitric acid and 1-5% of tartaric acid by mass percent, and the acid activation treatment time is 5-30 s;
preferably, the zinc dipping solution contains 15-30 g/L of zinc oxide, 80-120 g/L of NaOH, 10-30 g/L of potassium sodium tartrate, 0.5-2 g/L of ferric trichloride and 0.5-1.5 g/L of nickel sulfate, and the zinc dipping treatment time is 30-60 s;
preferably, the pyrophosphate copper plating solution contains 50-100 g/L of copper pyrophosphate, 200-400 g/L of potassium pyrophosphate, 5-20 g/L of ammonium citrate and 1-5 g/L of glycerol, the anode of the pyrophosphate copper plating is electrolytic copper, the plating temperature is 40-70 ℃, and the cathode current density is 1-6A/dm 2 The time is 3-30 min;
preferably, the methylsulfonate lead-tin-plating rare earth alloy solution contains 80 to 120g/L lead methylsulfonate, 5 to 20g/L stannous methylsulfonate, 60 to 120g/L methanesulfonic acid and 2 to 10g/L CeO 2 1-10 ml/L emulsifier and 0.05-1 g/L PVP; the anode of the methylsulfonate lead-tin-plated rare earth alloy is lead-tin alloy, and the cathode current density is 1-5A/dm 2 The electroplating temperature is 20-50 ℃ and the time is 10-90 min;
preferably, the lead bismuth antimony-rare earth nano cobalt powder solution plated by the fluoboric acid system contains 150-300 g/L of lead acetate, 50-200 g/L of fluoboric acid, 2-12 g/L of potassium antimony tartrate and 2-10 g/L of CeO 2 1-6 g/L of nano cobalt powder, 0.05-2 g/L of gelatin and 0.05-1 g/L of polyethylene glycol 6000, wherein the anode of the lead bismuth antimony-rare earth nano cobalt powder plated in the fluoboric acid system is lead antimony alloy, and the cathode current density is 3-10A/dm 2 The electroplating temperature is 20-60 ℃ and the time is 30-120 min;
preferably, the temperature for processing the extrusion drawing composite rod is 100-300 ℃, and the traction speed is 1-10 m/min;
preferably, the pickling solution contains 50-300 g/L of sodium acetate, 10-200 g/L of glucose and 1-20 g/L of tartaric acid;
preferably, the temperature of the heat treatment is 300 to 500 ℃ and the time is 3 to 5min.
Preferably, the method for treating the aluminum-titanium-boron composite particles coated with lead and silver on the sprayed surfaces comprises the following specific steps:
s1, removing oil from aluminum-titanium-boron particles by using sodium hydroxide solution, and sequentially performing HNO (hydrogen sulfide) treatment on the aluminum-titanium-boron particles 3 Solution activation, HCl solution coarsening, stannous chloride solution sensitization, silver nitrate solution or PdCl 2 Activating the solution to obtain pretreated Al-Ti-B particles;
preferably, the concentration of the sodium hydroxide solution is 5-10%, and the HNO is 3 The concentration of the solution is 5-10%, the concentration of HCl solution is 5-10%, the concentration of stannous chloride solution is 10-30 g/L, the concentration of silver nitrate solution is 1-3 g/L, pdCl 2 The concentration of the solution is 0.05-0.3 g/L;
s2, placing the pretreated aluminum-titanium-boron particles into chemical lead-silver plating solution for chemical composite plating, washing with deionized water, and performing solid-liquid separation to obtain lead-silver coated aluminum-titanium-boron composite particles;
preferably, the chemical lead-plating silver solution contains 10-20 g/L PbCl 2 10 to 40g/L of nitrilotriacetic acid, 10 to 50g/L of sodium citrate and 3 to 10ml/L of TiCl 3 (the mass concentration is 20 percent) and 1-5 g/L of nano silver powder, the pH value of the chemical lead-plating silver solution is 7.0-8.0, and the chemical composite plating time is 30-120 min;
and S3, spraying the lead-silver coated aluminum-titanium-boron composite particles on the surface of the extrusion drawing composite rod.
2) Welding a copper-aluminum composite conductive head and one end of an aluminum conductive beam, welding an anode composite rod on the bottom end of the aluminum conductive beam to form a fence-type aluminum-based composite anode plate support, horizontally die-casting multiple layers of conductive reinforcing ribs on the fence-type aluminum-based composite anode plate support, installing insulating sheaths on two sides of the fence-type aluminum-based composite anode plate support, and installing insulators on the fence-type aluminum-based composite anode plate support to obtain the energy-saving high-strength fence-type composite anode plate for non-ferrous metal electrodeposition.
The preparation method of the aluminum conductive beam comprises the following specific steps:
s1, sensitizing and activating glass fiber cloth, immersing the glass fiber cloth into an alkaline chemical tinning solution for tinning for 5-30 min, and then putting the glass fiber cloth into the alkaline electroplating lead-tin solution for electroplating lead-tin alloy for 0.5-8 h to obtain a glass fiber cloth surface coating lead-tin alloy composite layer;
the sensitizing solution is stannous chloride solution, the sensitizing temperature is 20-40 ℃, and the sensitizing time is 2-20 min;
the activation solution is silver nitrate solution, the activation temperature is 10-30 ℃, and the activation time is 2-10 min;
preferably, the alkaline chemical tinning solution contains 50-150 g/L of sodium stannate and 10-30 g/L of potassium hydroxide, the pH value of the alkaline chemical tinning solution is 10-12, and the tinning temperature is 50-70 ℃;
preferably, the alkaline lead-tin plating solution contains 10-30 g/L of lead oxide, 20-40 g/L of sodium stannate, 60-200 g/L of potassium sodium tartrate and 10-40 g/L of disodium ethylene diamine tetraacetate, the pH value of the alkaline lead-tin plating solution is 11-13, the temperature of the lead-tin alloy plating is 30-50 ℃, and the current density is 0.5-2A/dm 2 ；
S2, carrying out surface sand blasting on the aluminum or aluminum alloy beam, then carrying out hydrochloric acid activation treatment, then placing the beam in an alkaline chemical tinning solution for tinning for 5-30 min, and then forming a cooling liquid circulating channel parallel to the aluminum or aluminum alloy beam in the aluminum or aluminum alloy beam to obtain a chemically tinned aluminum or aluminum alloy beam;
preferably, the mass concentration of the hydrochloric acid is 5-20%, and the activation treatment time of the hydrochloric acid is 0.5-10 min;
preferably, the alkaline chemical tinning solution contains 50-150 g/L sodium stannate and 10-30 g/L potassium hydroxide, the pH value of the alkaline chemical tinning solution is 10-12, and the tinning temperature is 50-70 ℃;
s3, coating a lead-tin alloy composite layer on the surface of the glass fiber cloth obtained in the step S1 and coating rosin oil on the chemical tinned aluminum or aluminum alloy beam obtained in the step S2, and then performing heat treatment and coating at the temperature of 100-200 ℃ to obtain the aluminum conductive beam.
The preparation method of the copper-aluminum composite conductive head comprises the following specific steps:
s1, immersing a copper matrix into an acidic chemical tinning solution after sulfuric acid pickling and deionized water cleaning, tinning for 20-60 min at the temperature of 40-80 ℃, and cleaning and drying with deionized water to obtain a chemical tinning copper matrix;
preferably, the copper matrix is a T1 red copper matrix;
preferably, the acidic chemical tinning solution contains 20-40 g/L stannous chloride, 10-40 g/L nitrilotriacetic acid, 40-80 g/L thiourea, 20-40 ml/L concentrated hydrochloric acid, 20-60 g/L sodium citrate and 20-60 g/L sodium hypophosphite, and the pH value of the acidic chemical tinning solution is 0.5-2;
s2, placing a chemical tinned copper matrix in a die cavity, extruding an aluminum alloy filling cavity at the temperature of 600-700 ℃, and performing constant-pressure cooling, crystallization, solidification and forming to obtain a copper-aluminum composite conductive head;
preferably, the extrusion pressure is 1 to 6MPa and the extrusion rate is 6 to 12 m/s.
The beneficial effects of the invention are:
(1) The energy-saving high-strength fence type composite anode plate for the non-ferrous metal electrodeposition has the advantages that the electro-catalytic activity is good, the strength is high, the service life is long, compared with the traditional lead-silver multi-element alloy, on the basis of not changing the structure of an electrolytic cell, the composition of an electrolyte and the operation specification, the service life of the prepared anode is prolonged by 1 time, manganese dioxide particles coated on the surface of the electrode are few, the cell voltage is reduced by more than 10%, the current efficiency is improved by more than 3%, the quality of a cathode product is high, and the current density in the electrolytic process can be improved by 1 time;
(2) The surface of the aluminum beam is well protected by adopting the aging-resistant and strong-corrosion-resistant glass fiber surface metallization, so that a large amount of aluminum sulfate crystal salt cannot be generated due to the exposure of aluminum in the electrolytic process, and the heat dissipation of the beam body is well protected;
(3) According to the invention, the circulating cooling liquid channel is arranged in the aluminum beam, and the anti-oxidation water is introduced to circularly cool the aluminum beam, so that the heating problem of the beam body is solved, the interface resistance of the whole beam can be reduced, and the conductivity of the beam body is improved;
(4) The anode composite rod can be manufactured by adopting full-automatic line production, has high degree of mechanization, can save labor cost and improve efficiency, has high degree of standardization, and ensures that the manufactured fence type anode plate has good consistency, thereby improving the consistency of current in the electrolytic process and improving the current efficiency;
(5) According to the invention, by utilizing the high hardness of the lead-bismuth-antimony alloy and the good catalytic activity of the rare earth and the nano cobalt powder, the lead-bismuth-antimony/rare earth-nano cobalt powder layer is electrodeposited in a fluoboric acid system in a compounding way, the deposition of current density can be increased, a thicker lead alloy coating is obtained, and the obtained fence type anode plate has high strength and good electrocatalytic activity;
(6) According to the invention, the composite particles are obtained by coating the aluminum-titanium-boron particles with the lead-silver alloy, and the electro-catalytic activity of the anode is greatly improved by utilizing the corrosion resistance and high conductivity of the aluminum-titanium-boron and the corrosion resistance and catalytic activity of the lead and the silver according to the characteristic that the electrochemical reaction occurs at the liquid interface.
Drawings
FIG. 1 is a schematic view of an energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition;
FIG. 2 isbase:Sub>A schematic sectional view taken along line A-A of FIG. 1;
FIG. 3 is a schematic cross-sectional view taken along line B-B of FIG. 1;
in the figure: the composite material comprises 1-aluminum conductive beam, 11-aluminum substrate, 12-glass fiber cloth surface composite lead-tin layer, 2-copper-aluminum composite conductive head, aluminum in 21-copper-aluminum composite conductive head, copper in 22-copper-aluminum composite conductive head, 3-fence type aluminum-based composite anode plate bracket, 4-insulating sheath, 5-insulator, 6-conductive reinforcing rib, 7-anode composite rod, 71-aluminum alloy, 72-transition layer, 73-lead bismuth antimony/rare earth-nano cobalt composite layer and 74-aluminum titanium boron particle surface cladding lead-silver composite coating.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
As shown in fig. 1 to 3, the energy-saving high-strength fence-type composite anode plate for non-ferrous metal electrodeposition of the invention comprises an aluminum conductive beam 1, wherein a copper-aluminum composite conductive head 2 is fixedly arranged at the end of the aluminum conductive beam 1, a fence-type aluminum-based composite anode plate support 3 is fixedly arranged at the bottom end of the aluminum conductive beam 1, a plurality of layers of horizontal conductive reinforcing ribs 6 are fixedly arranged on the fence-type aluminum-based composite anode plate support 3 along the longitudinal direction, two sides of the fence-type aluminum-based composite anode plate support 3 are coated with insulating sheaths 4, and two ends of the conductive reinforcing ribs 6 are arranged in the insulating sheaths 4;
the fence type aluminum-based composite anode plate bracket 3 consists of a plurality of parallel anode composite rods 7, wherein each anode composite rod 7 sequentially comprises an aluminum alloy rod 71, a transition layer 72, a lead bismuth antimony/rare earth-nano cobalt composite layer 73 and an aluminum titanium boron particle surface coating lead silver composite coating 74 from inside to outside; the transition layer 72 sequentially comprises a zinc layer, a copper layer and a lead-tin-rare earth composite layer from inside to outside;
the thickness of the zinc layer in the transition layer 72 is 0.5-2 μm, the thickness of the copper layer is 3-8 μm, and the thickness of the lead-tin-rare earth composite layer is 4-20 μm; the mass percentage of tin in the lead-tin-rare earth composite layer is 5-30%, the mass percentage of rare earth is 0.01-0.5%, and the balance is lead; based on the mass fraction of the lead bismuth antimony/rare earth-nano cobalt composite layer 73 as 100%, bismuth accounts for 0.01-1%, antimony accounts for 0.5-5%, rare earth accounts for 0.01-0.1%, nano cobalt accounts for 0.01-0.5%, and the balance is Pb; in the lead-silver composite plating layer 74 coated on the surface of the aluminum-titanium-boron particles, the granularity of the aluminum-titanium-boron particles is 0.05-0.5 mm, and the thickness of the lead-silver composite plating layer is 0.1-0.6 mm; by taking the mass fraction of the lead-silver composite plating layer 74 coated on the surface of the aluminum-titanium-boron particles as 100%, 5-12% of lead, 0.5-3.0% of silver, 1-5% of titanium, 0.1-1% of boron and the balance of aluminum are contained in the aluminum-titanium-boron particles;
the copper-aluminum composite conductive head 2 consists of an inner layer copper bar 22 and an aluminum cladding layer 21; the copper bar 22 of the inner layer in the copper-aluminum composite conductive head 2 is of an isomeric structure, and the thickness is 5-20 mm; the aluminum cladding layer 21 comprises a tin transition layer and an aluminum surface layer, the thickness of the tin transition layer is 1-10 mu m, and the thickness of the aluminum surface layer is 5-30 mm;
the aluminum conductive beam 1 sequentially comprises aluminum or aluminum alloy, glass fiber cloth and a lead-tin layer from inside to outside;
a cooling liquid circulating channel parallel to the aluminum conductive beam 1 is formed in the aluminum conductive beam 1, and cooling liquid is filled in the cooling liquid circulating channel; the height of the aluminum conductive beam 1 is 10-60 mm, the thickness is 10-40 mm, the thickness of the glass fiber cloth is 0.2-2 mm, the thickness of the lead-tin layer is 0.1-2 mm, and the diameter of the cooling liquid circulation channel is 0.5-10 mm;
the conductive reinforcing rib 6 is a lead-tin-antimony alloy reinforcing rib, and by taking the mass fraction of the lead-tin-antimony alloy as 100%, lead accounts for 88-98%, tin accounts for 1-6%, and antimony accounts for 1-6%; the width of the conductive reinforcing rib 6 is 10-100 mm, and the thickness is 6-20 mm;
the preparation method of the energy-saving high-strength fence type composite anode plate for the non-ferrous metal electrodeposition comprises the following specific steps:
1) Sequentially carrying out alkali washing, deionized water washing, ultrasonic cleaning, acid activation treatment, deionized water washing, zinc dipping treatment, deionized water washing, pyrophosphate copper plating treatment, deionized water washing, methylsulfonate lead-tin rare earth alloy plating treatment, deionized water washing, lead-bismuth-antimony-rare earth nano cobalt powder plating treatment of a fluoboric acid system, deionized water washing, extrusion drawing composite rod treatment, acid washing for oil removal, deionized water washing and drying, spraying aluminum-titanium-boron composite particles with surfaces coated with lead and silver, carrying out heat treatment, taking up and carrying out fixed-length shearing on an aluminum wire to obtain an anode composite rod;
2) Welding a copper-aluminum composite conductive head and one end of an aluminum conductive beam, welding an anode composite rod on the bottom end of the aluminum conductive beam to form a fence-type aluminum-based composite anode plate support, horizontally die-casting multiple layers of conductive reinforcing ribs on the fence-type aluminum-based composite anode plate support, installing insulating sheaths on two sides of the fence-type aluminum-based composite anode plate support, and installing insulators on the fence-type aluminum-based composite anode plate support to obtain the energy-saving high-strength fence-type composite anode plate for non-ferrous metal electrodeposition.
The invention introduces the aging-resistant and corrosion-resistant glass fiber surface metalized lead alloy layer to coat the beam body, thereby preventing the conductive beam body from crystallizing and improving the heat dissipation performance; active silver nanoparticles are introduced to the working surface of the anode to coat the aluminum-titanium-boron composite particles with good conductivity and strong hardness, so that the electrocatalytic activity of the anode is improved and the service life of the anode is prolonged; compared with the traditional lead-silver multi-element alloy, on the basis of not changing the structure of an electrolytic cell, the composition of an electrolyte and the operation specification, the service life of the anode prepared by the invention is prolonged by 1 time, the manganese dioxide particles coated on the surface of the electrode are few, the cell voltage is reduced by more than 10%, the current efficiency is improved by more than 3%, the quality of a cathode product is high, and the current density in the electrolytic process can be improved by 1 time.
Example 1: the energy-saving high-strength fence type composite anode plate for nonferrous metal electrodeposition (see figures 1-3) is disclosed in the embodiment; the aluminum-copper composite conductive structure comprises an aluminum conductive beam 1, wherein a copper-aluminum composite conductive head 2 is fixedly arranged at the end of the aluminum conductive beam 1, a fence-type aluminum-based composite anode plate support 3 is fixedly arranged at the bottom end of the aluminum conductive beam 1, a plurality of layers of horizontal conductive reinforcing ribs 6 are fixedly arranged on the fence-type aluminum-based composite anode plate support 3 along the longitudinal direction, insulating sheaths 4 are coated on two sides of the fence-type aluminum-based composite anode plate support 3, and two ends of each conductive reinforcing rib 6 are arranged in the corresponding insulating sheaths 4; the insulating sheath 4 is used for fixing the edge of the fence type composite anode plate support, the insulator is used for fixing the inside of the fence type composite anode plate support, and the conductive reinforcing ribs 6 are used for fixing the anode composite rods of the fence type composite anode plate support;
the fence type aluminum-based composite anode plate bracket 3 consists of a plurality of parallel anode composite rods 7, wherein each anode composite rod 7 sequentially comprises an aluminum alloy rod 71, a transition layer 72, a lead-bismuth-antimony/rare earth-nano cobalt composite layer 73 and an aluminum-titanium-boron particle surface coated lead-silver composite coating 74 from inside to outside; the transition layer 72 sequentially comprises a zinc layer, a copper layer and a lead-tin-rare earth composite layer from inside to outside;
the thickness of the zinc layer in the transition layer 72 is 1 μm, the thickness of the copper layer is 5 μm, and the thickness of the lead-tin-rare earth composite layer is 15 μm; the mass percentage of tin in the lead-tin-rare earth composite layer is 20%, the mass percentage of rare earth is 0.2%, and the balance is lead; by taking the mass fraction of the lead bismuth antimony/rare earth-nano cobalt composite layer 73 as 100%, bismuth accounts for 0.5%, antimony accounts for 3%, rare earth accounts for 0.06%, nano cobalt accounts for 0.2%, and the balance is Pb; in the lead-silver composite plating layer 74 coated on the surface of the aluminum-titanium-boron particles, the granularity of the aluminum-titanium-boron particles is 0.2mm, and the thickness of the lead-silver composite plating layer is 0.25mm; by taking the mass fraction of the lead-silver composite plating layer 74 coated on the surface of the aluminum-titanium-boron particles as 100%, lead accounts for 8%, silver accounts for 2.0% (silver is 20nm nano silver powder), titanium accounts for 3%, boron accounts for 0.5%, and the balance is aluminum;
the copper-aluminum composite conductive head 2 is prepared by a die-casting method and consists of an inner layer copper bar 22 and an aluminum cladding layer 21; the copper bar 22 of the inner layer in the copper-aluminum composite conductive head 2 is of an isomeric structure, and the thickness is 10mm; the aluminum cladding layer 21 comprises a tin transition layer and an aluminum surface layer, the thickness of the tin transition layer is 2 mu m, and the thickness of the aluminum surface layer is 10mm;
the aluminum conductive beam 1 sequentially comprises 6061 aluminum alloy, glass fiber cloth and a lead-tin layer from inside to outside; a cooling liquid circulating channel parallel to the aluminum conductive beam 1 is formed in the aluminum conductive beam 1, and anti-oxidation circulating water is filled in the cooling liquid circulating channel to cool the aluminum conductive beam; the height of the aluminum conductive beam 1 is 40mm, the thickness of the aluminum conductive beam is 20mm, the thickness of the glass fiber cloth is 1mm, the thickness of the lead-tin layer is 1.5mm, and the diameter of the cooling liquid circulating channel is 5mm;
the conductive reinforcing ribs 6 are lead-tin-antimony alloy reinforcing ribs, and by taking the mass fraction of the lead-tin-antimony alloy as 100%, lead accounts for 95%, tin accounts for 3%, and antimony accounts for 2%; the width of the conductive reinforcing rib 6 is 60mm, and the thickness is 10mm;
the preparation method of the energy-saving high-strength fence type composite anode plate for the non-ferrous metal electrodeposition comprises the following specific steps:
1) Preparing an aluminum conductive beam: the preparation method of the aluminum conductive beam comprises the following specific steps:
s1, sensitizing and activating glass fiber cloth at room temperature for 14min, then immersing the glass fiber cloth into an alkaline chemical tinning solution for tinning for 15min, and then putting the glass fiber cloth into the alkaline electroplating lead-tin solution for electroplating lead-tin alloy for 4h to obtain a glass fiber cloth surface coating lead-tin alloy composite layer;
wherein the sensitizing solution is 20g/LSnCI 2 +20ml/LHCl solution, sensitization time 7min;
the activating solution is 1g/L PdCl 2 Ultrasonic activating for 7min;
the alkaline chemical tinning solution contains 100g/L sodium stannate and 20g/L potassium hydroxide, the pH value of the alkaline chemical tinning solution is 11, the tinning temperature is 60 ℃, and the mechanical stirring speed is 200rpm;
the alkaline lead-tin plating solution contains 20g/L lead oxide, 30g/L sodium stannate, 120g/L potassium sodium tartrate and 30g/L disodium ethylene diamine tetraacetate, the pH value of the alkaline lead-tin plating solution is 12, the temperature of the electroplated lead-tin alloy is 40 ℃, and the current density is 1A/dm 2 ；
S2, carrying out sand blasting on the surface of the aluminum beam through 60-mesh SiC, then carrying out hydrochloric acid activation treatment, then placing the aluminum beam in an alkaline chemical tinning solution for tinning for 15min, and then forming a cooling liquid circulation channel parallel to the aluminum or aluminum alloy beam in the aluminum beam to obtain a chemical tinning aluminum beam; wherein the mass concentration of the hydrochloric acid is 10%, and the activation treatment time of the hydrochloric acid is 5min; the alkaline chemical tinning solution contains 100g/L sodium stannate and 20g/L potassium hydroxide, the pH value of the alkaline chemical tinning solution is 11, the tinning temperature is 60 ℃, and the mechanical stirring speed is 200rpm;
s3, coating a lead-tin alloy composite layer on the surface of the glass fiber cloth obtained in the step S1 and coating rosin oil on the chemical tinned aluminum or aluminum alloy beam obtained in the step S2, and then performing heat treatment at the temperature of 150 ℃ to coat to obtain an aluminum conductive beam;
2) Preparing a copper-aluminum composite conductive head: the preparation method of the copper-aluminum composite conductive head comprises the following specific steps:
s1, pickling a T1 red copper matrix with sulfuric acid with the concentration of 20% and washing the red copper matrix with deionized water, then soaking the red copper matrix into an acidic chemical tinning solution, tinning the red copper matrix for 40min at the temperature of 60 ℃, and washing and drying the red copper matrix with deionized water to obtain a chemical tinning copper matrix;
wherein the acidic chemical tinning solution contains 30g/L stannous chloride, 30g/L nitrilotriacetic acid, 60g/L thiourea, 30ml/L concentrated hydrochloric acid sold in the market, 40g/L sodium citrate and 40g/L sodium hypophosphite, and the pH value of the acidic chemical tinning solution is maintained at 1.0;
s2, placing a chemical tinned copper substrate in a die cavity, extruding an aluminum alloy filling cavity at the temperature of 670 ℃, cooling at constant pressure, crystallizing, solidifying and forming to obtain a copper-aluminum composite conductive head; wherein the extrusion pressure is 4MPa, and the extrusion speed is 8 m/s;
3) Sequentially carrying out alkali washing, deionized water washing, ultrasonic cleaning, acid activation treatment, deionized water washing, zinc dipping treatment, deionized water washing, pyrophosphate copper plating treatment, deionized water washing, methylsulfonate lead-tin rare earth alloy plating treatment, deionized water washing, lead-bismuth-antimony-rare earth nano cobalt powder plating treatment of a fluoboric acid system, deionized water washing, extrusion drawing composite rod treatment, acid washing for oil removal, deionized water washing and drying, spraying aluminum-titanium-boron composite particles with surfaces coated with lead and silver, carrying out heat treatment, taking up and carrying out fixed-length shearing on an aluminum wire to obtain an anode composite rod;
wherein the alkaline washing liquid contains 60g/L NaOH and 10g/L Na 2 CO 3 The alkali washing temperature is 60 ℃, and the alkali washing soaking time is 60s;
the acid activation solution contains 40% of nitric acid and 3% of tartaric acid by mass percent, and the acid activation treatment time is 18s;
the zinc dipping solution contains 20g/L of zinc oxide, 100g/L of NaOH, 20g/L of potassium sodium tartrate, 1.0g/L of ferric trichloride and 1.0g/L of nickel sulfate, and the zinc dipping treatment time is 40s;
the pyrophosphate copper plating solution contains 60g/L of copper pyrophosphate, 300g/L of potassium pyrophosphate, 16g/L of ammonium citrate and 3g/L of glycerol, the anode of the pyrophosphate copper plating is copper, the electroplating temperature is 50 ℃, and the cathode current density is 3A/dm 2 The time is 20min;
the methylsulfonate lead-tin-plating rare earth alloy solution contains 100g/L lead methylsulfonate, 12g/L stannous methylsulfonate, 100g/L methanesulfonic acid and 6g/L CeO 2 6ml/L of emulsifier (OP-10 as emulsifier) and 0.5g/L of PVP; the anode of the methylsulfonate lead-tin-plated rare earth alloy is Pb-3% Sn alloy, and the cathode current density is 3A/dm 2 The electroplating temperature is 40 ℃ and the time is 60min;
the lead bismuth antimony rare earth nano cobalt powder solution plated by the fluoboric acid system contains 200g/L lead acetate, 100g/L fluoboric acid, 8g/L antimony potassium tartrate and 6g/L CeO 2 3g/L of nano cobalt powder, 1g/L of gelatin and 0.5g/L of polyethylene glycol 6000; the anode of the lead bismuth antimony-rare earth nano cobalt powder plated by the fluoboric acid system is Pb-1.5 percent of Sb alloy and the cathode current density is 6A/dm 2 Electroplating at 40 deg.C for 90min;
the extrusion drawing composite rod processing is carried out in an extrusion coating machine, the temperature of a die is 200 ℃, and the traction speed is 6m/min;
the pickling solution contains 180g/L of sodium acetate, 100g/L of glucose and 10g/L of tartaric acid;
the heat treatment is carried out for 5min in a hot-blast stove with the temperature of 420 ℃;
the method for treating the aluminum-titanium-boron composite particles coated with lead and silver on the surfaces by spraying comprises the following specific steps:
s1, removing oil from aluminum-titanium-boron particles by using sodium hydroxide solution, and sequentially performing HNO 3 Activating the solution for 2min, coarsening the HCl solution for 5min, sensitizing the stannous chloride solution for 10min and activating the silver nitrate solution for 5min to obtain pretreated aluminum-titanium-boron particles;
sodium hydroxide solution concentration of 7%, HNO 3 The concentration of the solution is 7 percent, the concentration of the HCl solution is 7 percent, and the concentration of the stannous chloride solution is 20g/LSnCI 2 +20ml/LHCl, and the concentration of silver nitrate solution is 3g/L;
s2, placing the pretreated aluminum-titanium-boron particles into chemical lead-silver plating solution for chemical composite plating, washing with deionized water, and performing solid-liquid separation to obtain lead-silver coated aluminum-titanium-boron composite particles;
the chemical lead-plating silver liquid contains 15g/L PbC1 2 30g/L nitrilotriacetic acid, 30g/L sodium citrate, 6ml/L TiCl 3 (the mass concentration is 20 percent) and 3g/L of nano silver powder, the pH value of the chemical lead-plating silver solution is adjusted to 8.0 by ammonia water, and the chemical composite plating time is 90min;
s3, spraying the aluminum-titanium-boron composite particles coated with the lead and the silver on the surface of the extrusion drawing composite rod by a cold spraying machine;
4) Welding a copper-aluminum composite conductive head and one end of an aluminum conductive beam, welding an anode composite rod on the bottom end of the aluminum conductive beam to form a fence-type aluminum-based composite anode plate support, horizontally die-casting multiple layers of conductive reinforcing ribs on the fence-type aluminum-based composite anode plate support, mounting insulating sheaths on two sides of the fence-type aluminum-based composite anode plate support, and mounting an insulator on the fence-type aluminum-based composite anode plate support to obtain the energy-saving high-strength fence-type composite anode plate for non-ferrous metal electrowinning;
the energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition is used in an acid zinc electrolyte under the electrolysis conditions that the concentration of zinc ions in the electrolyte is 50g/L, the concentration of sulfuric acid is 160g/L, and Mn is contained in the electrolyte 2+ Is 12g/L, and has a current density of 800A/m 2 The electrolysis temperature is 40 ℃, the electrical efficiency of the gradient composite lead dioxide anode is improved by 5.0 percent compared with the traditional lead-calcium (0.06 percent) silver (0.3 percent) alloy anode plate, the cell voltage is reduced by 15 percent, the service life is prolonged by 2.5 times, and the manganese dioxide particles coated on the surface of the electrode are reduced by 80 percent.
Example 2: the energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition in the embodiment has basically the same structure as the energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition in the embodiment 1, and the difference lies in that: the thickness of the zinc layer in the transition layer 72 is 0.5 mu m, the thickness of the copper layer is 3 mu m, and the thickness of the lead-tin-rare earth composite layer is 4 mu m; the mass percent of tin in the lead-tin-rare earth composite layer is 5%, the mass percent of rare earth is 0.01%, and the balance is lead; by taking the mass fraction of the lead bismuth antimony/rare earth-nano cobalt composite layer 73 as 100%, bismuth accounts for 0.01%, antimony accounts for 0.5%, rare earth accounts for 0.01%, nano cobalt accounts for 0.01%, and the balance is Pb; in the lead-silver composite plating layer 74 coated on the surface of the aluminum-titanium-boron particles, the granularity of the aluminum-titanium-boron particles is 0.05mm, and the thickness of the lead-silver composite plating layer is 0.1mm; the mass fraction of the lead-silver composite coating 74 coated on the surface of the aluminum-titanium-boron particle is 100%, the lead accounts for 5%, the silver accounts for 0.5% (silver is 10nm nano silver powder), the titanium accounts for 1%, the boron accounts for 0.1%, and the balance is aluminum;
the copper-aluminum composite conductive head 2 is prepared by a die-casting method and consists of an inner layer copper bar 22 and an aluminum cladding layer 21; the copper bar 22 of the inner layer in the copper-aluminum composite conductive head 2 is of an isomeric structure, and the thickness is 5mm; the aluminum cladding layer 21 comprises a tin transition layer and an aluminum surface layer, the thickness of the tin transition layer is 1 mu m, and the thickness of the aluminum surface layer is 5mm;
the aluminum conductive beam 1 sequentially comprises 6061 aluminum alloy, glass fiber cloth and a lead-tin layer from inside to outside; a cooling liquid circulating channel parallel to the aluminum conductive beam 1 is formed in the aluminum conductive beam 1, and anti-oxidation circulating water is filled in the cooling liquid circulating channel to cool the aluminum conductive beam; the height of the aluminum conductive beam 1 is 20mm, the thickness of the aluminum conductive beam is 10mm, the thickness of the glass fiber cloth is 0.2mm, the thickness of the lead-tin layer is 0.1mm, and the diameter of the cooling liquid circulating channel is 0.5mm;
the conductive reinforcing ribs 6 are lead-tin-antimony alloy reinforcing ribs, and lead accounts for 98%, tin accounts for 1% and antimony accounts for 1% by taking the mass fraction of the lead-tin-antimony alloy as 100%; the width of the conductive reinforcing rib 6 is 10mm, and the thickness of the conductive reinforcing rib is 6mm;
the preparation method of the energy-saving high-strength fence type composite anode plate for nonferrous metal electrodeposition comprises the following specific steps:
1) Preparing an aluminum conductive beam: the preparation method of the aluminum conductive beam comprises the following specific steps:
s1, sensitizing and activating glass fiber cloth at room temperature, then immersing the glass fiber cloth into an alkaline chemical tinning solution for tinning for 5min, and then putting the glass fiber cloth into the alkaline electroplating lead-tin solution for electroplating lead-tin alloy for 0.5h to obtain a glass fiber cloth surface coating lead-tin alloy composite layer;
wherein the sensitizing solution is 10g/LSnCI 2 +10ml/L HCl solution, sensitization time is 2min;
the activating solution is 0.2g/L PdCl 2 Ultrasonic activating for 2min;
the alkaline chemical tinning solution contains 50g/L sodium stannate and 10g/L potassium hydroxide, the pH value of the alkaline chemical tinning solution is 10, the tinning temperature is 50 ℃, and the mechanical stirring speed is 100rpm;
the alkaline lead-tin plating solution contains 10g/L lead oxide, 20g/L sodium stannate, 60g/L potassium sodium tartrate and 10g/L ethylene diamine tetraacetic acid disodium, the pH value of the alkaline lead-tin plating solution is 11, the temperature of the lead-tin alloy plating is 30 ℃, and the current density is 0.5A/dm 2 ；
S2, performing hydrochloric acid activation treatment on the aluminum beam after sand blasting is performed on the surface of 200-mesh SiC, then placing the aluminum beam in an alkaline chemical tinning solution for tinning for 5min, and then forming a cooling liquid circulating channel parallel to the aluminum or aluminum alloy beam in the aluminum beam to obtain a chemical tinning aluminum beam; wherein the mass concentration of the hydrochloric acid is 10 percent, and the activation treatment time of the hydrochloric acid is 0.5min; the alkaline chemical tinning solution contains 50g/L sodium stannate and 10g/L potassium hydroxide, the pH value of the alkaline chemical tinning solution is 10, the tinning temperature is 50 ℃, and the mechanical stirring speed is 100rpm;
s3, coating a lead-tin alloy composite layer on the surface of the glass fiber cloth obtained in the step S1 and coating rosin oil on the chemically tinned aluminum or aluminum alloy beam obtained in the step S2, and then performing heat treatment and coating at the temperature of 100 ℃ to obtain an aluminum conductive beam;
2) Preparing a copper-aluminum composite conductive head: the preparation method of the copper-aluminum composite conductive head comprises the following specific steps:
s1, immersing a T1 red copper matrix into an acidic chemical tinning solution after pickling with sulfuric acid with the concentration of 10% and cleaning with deionized water, tinning for 20min at the temperature of 40 ℃, and cleaning and drying with deionized water to obtain a chemical tinned copper matrix;
wherein the acidic chemical tinning solution contains 20g/L stannous chloride, 10g/L nitrilotriacetic acid, 40g/L thiourea, 20ml/L concentrated hydrochloric acid sold in the market, 20g/L sodium citrate and 20g/L sodium hypophosphite, and the pH value of the acidic chemical tinning solution is maintained at 0.5;
s2, placing a chemical tinned copper substrate in a die cavity, extruding an aluminum alloy filling cavity at the temperature of 600 ℃, cooling at constant pressure, crystallizing, solidifying and forming to obtain a copper-aluminum composite conductive head; wherein the extrusion pressure is 1MPa, and the extrusion speed is 6 m/s;
3) Preparing the anode composite rod by adopting a full-automatic flow production line process flow: sequentially carrying out alkali washing, deionized water washing, ultrasonic cleaning, acid activation treatment, deionized water washing, zinc dipping treatment, deionized water washing, pyrophosphate copper plating treatment, deionized water washing, methylsulfonate lead-tin rare earth alloy plating treatment, deionized water washing, lead-bismuth-antimony-rare earth nano cobalt powder plating treatment of a fluoboric acid system, deionized water washing, extrusion and drawing composite rod treatment, acid washing and oil removal, deionized water washing and drying, spraying aluminum-titanium-boron composite particles with surfaces coated with lead and silver, carrying out heat treatment, taking up wires and carrying out fixed-length shearing on the aluminum wires to obtain an anode composite rod;
wherein the alkaline washing liquid contains 10g/L NaOH and 5g/L Na 2 CO 3 The alkali washing temperature is 50 ℃, and the alkali washing soaking time is 20s;
the acid activation solution contains 20% of nitric acid and 1% of tartaric acid by mass percent, and the acid activation treatment time is 5s;
the zinc dipping solution contains 15g/L of zinc oxide, 80g/L of NaOH, 10g/L of potassium sodium tartrate, 0.5g/L of ferric trichloride and 0.5g/L of nickel sulfate, and the zinc dipping treatment time is 30s;
the pyrophosphate copper plating solution contains 50g/L of copper pyrophosphate, 200g/L of potassium pyrophosphate, 5g/L of ammonium citrate and 1g/L of glycerol, the anode of pyrophosphate copper plating is red copper T1, the electroplating temperature is 40 ℃, and the cathode current density is 1A/dm 2 The time is 3min;
the methylsulfonate lead-tin-plating rare earth alloy solution contains 80g/L lead methylsulfonate, 5g/L stannous methylsulfonate, 60g/L methanesulfonic acid and 2g/L CeO 2 1ml/L emulsifier (OP-10 as emulsifier) and 0.05g/L PVP; anode of methylsulfonate lead-tin rare earth alloy is Pb-1% Sn alloy, cathode current density is 1A/dm 2 Electroplating at 20 deg.C for 10min;
the lead bismuth antimony rare earth nano cobalt powder solution plated by the fluoboric acid system contains 150g/L lead acetate,50g/L of fluoroboric acid, 2g/L of antimony potassium tartrate and 2g/L of CeO 2 1g/L of nano cobalt powder, 0.05g/L of gelatin and 0.05g/L of polyethylene glycol 6000; the anode of the lead bismuth antimony-rare earth nano cobalt powder plated by the fluoboric acid system is Pb-0.5 percent of Sb alloy and the cathode current density is 6A/dm 2 Electroplating temperature is 20 deg.C and time is 30min;
the extrusion drawing composite rod processing is carried out in an extrusion coating machine, the temperature of a die is 100 ℃, and the traction speed is 1m/min;
the pickling solution contains 50g/L sodium acetate, 10g/L glucose and 1g/L tartaric acid;
the heat treatment is carried out in a hot blast stove at the temperature of 300 ℃ for 3min;
the method for treating the aluminum-titanium-boron composite particles coated with lead and silver on the surfaces by spraying comprises the following specific steps:
s1, removing oil from aluminum-titanium-boron particles by using sodium hydroxide solution, and sequentially performing HNO 3 Activating the solution for 1min, coarsening the HCl solution for 1min, sensitizing the stannous chloride solution for 5min and activating the silver nitrate solution for 3min to obtain pretreated aluminum-titanium-boron particles;
sodium hydroxide solution concentration of 5%, HNO 3 The concentration of the solution is 5 percent, the concentration of the HCl solution is 5 percent, and the concentration of the stannous chloride solution is g/LSnCI 2 +5ml/LHCl, silver nitrate solution concentration of 1g/L;
s2, placing the pretreated aluminum-titanium-boron particles in a chemical lead-silver plating solution for chemical composite plating, washing with deionized water, and performing solid-liquid separation to obtain lead-silver coated aluminum-titanium-boron composite particles;
the chemical lead-plating silver solution contains 10g/L PbC1 2 10g/L nitrilotriacetic acid, 10g/L sodium citrate, 3ml/L TiCl 3 (the mass concentration is 20%) and 1g/L of nano silver powder, adjusting the pH value of the chemical lead-plating silver solution to 7.0 by ammonia water, and carrying out chemical composite plating for 30min;
s3, spraying the aluminum-titanium-boron composite particles coated with lead and silver on the surface of the extrusion drawing composite rod by a cold spraying machine;
4) Welding a copper-aluminum composite conductive head and one end of an aluminum conductive beam, welding an anode composite rod on the bottom end of the aluminum conductive beam to form a fence-type aluminum-based composite anode plate support, horizontally die-casting multiple layers of conductive reinforcing ribs on the fence-type aluminum-based composite anode plate support, mounting insulating sheaths on two sides of the fence-type aluminum-based composite anode plate support, and mounting an insulator on the fence-type aluminum-based composite anode plate support to obtain the energy-saving high-strength fence-type composite anode plate for non-ferrous metal electrowinning;
the energy-saving high-strength fence type composite anode plate for nonferrous metal electrodeposition is used in acid zinc electrolyte, and the electrolysis conditions are that the concentration of zinc ions in the electrolyte is 50g/L, the concentration of sulfuric acid is 160g/L, and Mn is contained in the electrolyte 2+ Is 12g/L, and has a current density of 700A/m 2 The electrolysis temperature is 40 ℃, the electrical efficiency of the gradient composite lead dioxide anode is improved by 3.0 percent compared with the traditional lead-calcium (0.06 percent) silver (0.3 percent) alloy anode plate, the cell voltage is reduced by 5 percent, the service life is prolonged by 1.2 times, and the manganese dioxide particles coated on the surface of the electrode are reduced by 40 percent.
Example 3: the energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition in the embodiment has basically the same structure as the energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition in the embodiment 1, and the difference lies in that: the thickness of a zinc layer in the transition layer 72 is 2 micrometers, the thickness of a copper layer is 8 micrometers, and the thickness of a lead-tin-rare earth composite layer is 20 micrometers; the mass percentage of tin in the lead-tin-rare earth composite layer is 30%, the mass percentage of rare earth is 0.5%, and the balance is lead; based on the mass fraction of the lead bismuth antimony/rare earth-nano cobalt composite layer 73 as 100%, bismuth accounts for 1.0%, antimony accounts for 5%, rare earth accounts for 0.1%, nano cobalt accounts for 0.5%, and the balance is Pb; in the lead-silver composite plating layer 74 coated on the surface of the aluminum-titanium-boron particles, the granularity of the aluminum-titanium-boron particles is 0.5mm, and the thickness of the lead-silver composite plating layer is 0.6mm; based on the mass fraction of the lead-silver composite coating 74 coated on the surface of the aluminum-titanium-boron particle being 100%, 12% of lead, 3% of silver (silver is 50nm nano silver powder), 5% of titanium, 1% of boron and the balance of aluminum in the aluminum-titanium-boron particle;
the copper-aluminum composite conductive head 2 is prepared by a die-casting method and consists of an inner layer copper bar 22 and an aluminum cladding layer 21; the copper bar 22 of the inner layer in the copper-aluminum composite conductive head 2 is of an isomeric structure, and the thickness is 20mm; the aluminum cladding layer 21 comprises a tin transition layer and an aluminum surface layer, the thickness of the tin transition layer is 10 mu m, and the thickness of the aluminum surface layer is 20mm;
the aluminum conductive beam 1 sequentially comprises 6061 aluminum alloy, glass fiber cloth and a lead-tin layer from inside to outside; a cooling liquid circulating channel parallel to the aluminum conductive beam 1 is formed in the aluminum conductive beam 1, and anti-oxidation circulating water is filled in the cooling liquid circulating channel to cool the aluminum conductive beam; the height of the aluminum conductive beam 1 is 60mm, the thickness of the aluminum conductive beam is 40mm, the thickness of the glass fiber cloth is 2mm, the thickness of the lead-tin layer is 2mm, and the diameter of the cooling liquid circulating channel is 10mm;
the conductive reinforcing ribs 6 are lead-tin-antimony alloy reinforcing ribs, and lead accounts for 88%, tin accounts for 6% and antimony accounts for 6% by taking the mass fraction of the lead-tin-antimony alloy as 100%; the width of the conductive reinforcing rib 6 is 100mm, and the thickness is 20mm;
the preparation method of the energy-saving high-strength fence type composite anode plate for the non-ferrous metal electrodeposition comprises the following specific steps:
1) Preparing an aluminum conductive beam: the preparation method of the aluminum conductive beam comprises the following specific steps:
s1, sensitizing and activating glass fiber cloth at room temperature, then immersing the glass fiber cloth into an alkaline chemical tinning solution for tinning for 30min, and then putting the glass fiber cloth into the alkaline electroplating lead-tin solution for electroplating lead-tin alloy for 8h to obtain a glass fiber cloth surface-coated lead-tin alloy composite layer;
wherein the sensitizing solution is 20g/LSnCI 2 +20ml/L HCl solution, and the sensitization time is 10min;
the activating solution is 3g/L AgNO 3 Ultrasonic activating for 10min;
the alkaline chemical tinning solution contains 150g/L sodium stannate and 30g/L potassium hydroxide, the pH value of the alkaline chemical tinning solution is 12, the tinning temperature is 70 ℃, and the mechanical stirring speed is 300rpm;
the alkaline lead-tin plating solution contains 30g/L lead oxide, 40g/L sodium stannate, 200g/L potassium sodium tartrate and 40g/L ethylene diamine tetraacetic acid disodium, the pH value of the alkaline lead-tin plating solution is 13, the temperature of the lead-tin alloy plating is 50 ℃, and the current density is 2A/dm 2 ；
S2, passing the aluminum beam through a 40-mesh A1 2 O 3 Carrying out hydrochloric acid activation treatment after sand blasting on the surface, then placing the beam in an alkaline chemical tinning solution for tinning for 30min, and then forming a cooling liquid circulating channel parallel to the aluminum or aluminum alloy beam in the aluminum beam to obtain a chemical tinning aluminum beam; wherein the mass concentration of the hydrochloric acid is 15%, and the activation treatment time of the hydrochloric acid is 10min; basic chemistryThe tin plating solution contains 150g/L sodium stannate and 30g/L potassium hydroxide, the pH value of the alkaline chemical tin plating solution is 12, the tin plating temperature is 70 ℃, and the mechanical stirring speed is 300rpm;
s3, coating a lead-tin alloy composite layer on the surface of the glass fiber cloth obtained in the step S1 and coating rosin oil on the chemically tinned aluminum or aluminum alloy beam obtained in the step S2, and then performing heat treatment and coating at the temperature of 200 ℃ to obtain an aluminum conductive beam;
2) Preparing a copper-aluminum composite conductive head: the preparation method of the copper-aluminum composite conductive head comprises the following specific steps:
s1, pickling a T1 red copper matrix with sulfuric acid with the concentration of 20% and washing the red copper matrix with deionized water, then immersing the red copper matrix into an acidic chemical tinning solution, tinning the red copper matrix for 60min at the temperature of 80 ℃, and washing and drying the red copper matrix with deionized water to obtain a chemical tinning copper matrix;
wherein the acidic chemical tinning solution contains 40g/L stannous chloride, 40g/L nitrilotriacetic acid, 80g/L thiourea, 40ml/L concentrated hydrochloric acid sold in the market, 60g/L sodium citrate and 60g/L sodium hypophosphite, and the pH value of the acidic chemical tinning solution is maintained at 2.0;
s2, placing a chemical tinned copper substrate in a die cavity, extruding an aluminum alloy filling cavity at the temperature of 700 ℃, cooling at constant pressure, crystallizing, solidifying and forming to obtain a copper-aluminum composite conductive head; wherein the extrusion pressure is 6MPa, and the extrusion speed is 12 m/s;
3) Sequentially carrying out alkali washing, deionized water washing, ultrasonic cleaning, acid activation treatment, deionized water washing, zinc dipping treatment, deionized water washing, pyrophosphate copper plating treatment, deionized water washing, methylsulfonate lead-tin rare earth alloy plating treatment, deionized water washing, lead-bismuth-antimony-rare earth nano cobalt powder plating treatment of a fluoboric acid system, deionized water washing, extrusion and drawing composite rod treatment, acid washing and oil removal, deionized water washing and drying, spraying aluminum-titanium-boron composite particles with surfaces coated with lead and silver, carrying out heat treatment, taking up wires and carrying out fixed-length shearing on the aluminum wires to obtain an anode composite rod;
wherein the alkaline washing solution contains 100g/L NaOH and 20g/L Na 2 CO 3 The alkali washing temperature is 70 ℃, and the alkali washing soaking time is 100s;
the acid activation solution contains 50% of nitric acid and 5% of tartaric acid by mass percent, and the acid activation treatment time is 30s;
the zinc dipping solution contains 30g/L of zinc oxide, 120g/L of NaOH, 30g/L of potassium sodium tartrate, 2g/L of ferric trichloride and 1.5g/L of nickel sulfate, and the zinc dipping treatment time is 60s;
the pyrophosphate copper plating solution contains 100g/L of copper pyrophosphate, 400g/L of potassium pyrophosphate, 20g/L of ammonium citrate and 5g/L of glycerol, the anode of the pyrophosphate copper plating is red copper T1, the electroplating temperature is 70 ℃, and the cathode current density is 6A/dm 2 The time is 30min;
the methylsulfonate lead-tin-plating rare earth alloy solution contains 120g/L lead methylsulfonate, 20g/L stannous methylsulfonate, 120g/L methanesulfonic acid and 10g/L CeO 2 10ml/L emulsifier (OP-10 as emulsifier) and 1.0g/L PVP; the anode of the methylsulfonate lead-tin-plated rare earth alloy is Pb-5% Sn alloy, and the cathode current density is 5A/dm 2 The electroplating temperature is 50 ℃ and the time is 90min;
the lead bismuth antimony-rare earth nano cobalt powder plating solution of the fluoboric acid system contains 300g/L of lead acetate, 200g/L of fluoboric acid, 12g/L of antimony potassium tartrate and 10g/L of CeO 2 6g/L of nano cobalt powder, 2g/L of gelatin and 1.0g/L of polyethylene glycol 6000; the anode of the lead bismuth antimony-rare earth nano cobalt powder plated by the fluoboric acid system is Pb-3 percent, the Sb alloy and the cathode current density are 6A/dm 2 Electroplating at 60 deg.C for 90min;
the extrusion drawing composite rod processing is carried out in an extrusion coating machine, the temperature of a die is 300 ℃, and the traction speed is 10m/min;
the pickling solution contains 300g/L of sodium acetate, 200g/L of glucose and 20g/L of tartaric acid;
the heat treatment is carried out in a hot-blast stove at the temperature of 500 ℃ for 5min;
the method for treating the aluminum-titanium-boron composite particles coated with lead and silver on the surfaces by spraying comprises the following specific steps:
s1, removing oil from aluminum-titanium-boron particles by using sodium hydroxide solution, and sequentially performing HNO 3 Activating the solution for 3min, coarsening the HCl solution for 4min, sensitizing the stannous chloride solution for 20min and PdCl 2 Activating the solution for 5min to obtain pretreated Al-Ti-B particles;
sodium hydroxide solution concentration of 10%, HNO 3 The concentration of the solution is 10 percent, the concentration of the HCl solution is 10 percent, and the concentration of the stannous chloride solution is 30g/LSnCI 2 +30ml/L HCl，PdCl 2 The concentration of the solution is 1g/L;
s2, placing the pretreated aluminum-titanium-boron particles into chemical lead-silver plating solution for chemical composite plating, washing with deionized water, and performing solid-liquid separation to obtain lead-silver coated aluminum-titanium-boron composite particles;
the chemical lead-plating silver solution contains 20g/L PbCl 2 40g/L nitrilotriacetic acid, 50g/L sodium citrate and 10ml/L TiCl 3 (the mass concentration is 20%) and 5g/L of nano silver powder, adjusting the pH value of the chemical lead-plating silver solution to 8.0 by ammonia water, and carrying out chemical composite plating for 120min;
s3, spraying the aluminum-titanium-boron composite particles coated with the lead and the silver on the surface of the extrusion drawing composite rod by a cold spraying machine;
4) Welding a copper-aluminum composite conductive head and one end of an aluminum conductive beam, welding an anode composite rod on the bottom end of the aluminum conductive beam to form a fence-type aluminum-based composite anode plate support, horizontally die-casting multiple layers of conductive reinforcing ribs on the fence-type aluminum-based composite anode plate support, mounting insulating sheaths on two sides of the fence-type aluminum-based composite anode plate support, and mounting an insulator on the fence-type aluminum-based composite anode plate support to obtain the energy-saving high-strength fence-type composite anode plate for non-ferrous metal electrowinning;
the energy-saving high-strength fence type composite anode plate for non-ferrous metal electrodeposition is used in an acid zinc electrolyte under the electrolysis conditions that the concentration of zinc ions in the electrolyte is 50g/L, the concentration of sulfuric acid is 160g/L, and Mn is contained in the electrolyte 2+ Is 12g/L, and has a current density of 1000A/m 2 The electrolytic temperature is 40 ℃, the electric efficiency of the fence type composite anode is improved by 3.0 percent compared with the traditional lead-calcium (0.06 percent) silver (0.3 percent) alloy anode plate, the cell voltage is reduced by 10 percent, the service life is prolonged by 1.5 times, and the manganese dioxide particles coated on the surface of the electrode are reduced by 60 percent.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. The utility model provides a non ferrous metal is energy-conserving high strength fence type composite anode plate for electrodeposition which characterized in that: the aluminum-copper composite conductive device comprises an aluminum conductive beam (1), wherein a copper-aluminum composite conductive head (2) is fixedly arranged at the end of the aluminum conductive beam (1), a fence-type aluminum-based composite anode plate support (3) is fixedly arranged at the bottom end of the aluminum conductive beam (1), a plurality of layers of horizontal conductive reinforcing ribs (6) are fixedly arranged on the fence-type aluminum-based composite anode plate support (3) along the longitudinal direction, an insulating sheath (4) is coated on two sides of the fence-type aluminum-based composite anode plate support (3), and two ends of each conductive reinforcing rib (6) are arranged in the insulating sheath (4);
the fence type aluminum-based composite anode plate bracket (3) consists of a plurality of parallel anode composite rods (7), wherein each anode composite rod (7) sequentially comprises an aluminum alloy rod (71), a transition layer (72), a lead bismuth antimony/rare earth-nano cobalt composite layer (73) and an aluminum titanium boron particle surface coated lead-silver composite coating (74) from inside to outside; the transition layer (72) comprises a zinc layer, a copper layer and a lead-tin rare earth composite layer from inside to outside in sequence.
2. The energy-saving high-strength fence type composite anode plate for nonferrous metal electrodeposition according to claim 1, wherein: the copper-aluminum composite conductive head (2) consists of an inner layer copper bar (22) and an aluminum coating layer (21).
3. The energy-saving high-strength fence type composite anode plate for nonferrous metal electrodeposition according to claim 1, wherein: the aluminum conductive beam (1) sequentially comprises aluminum or aluminum alloy, glass fiber cloth and a lead-tin layer from inside to outside.
4. The energy-saving high-strength fence type composite anode plate for the non-ferrous metal electrodeposition as claimed in claim 1 or 3, wherein: a cooling liquid circulating channel parallel to the aluminum conductive beam (1) is formed in the aluminum conductive beam (1), and cooling liquid is filled in the cooling liquid circulating channel.
5. The energy-saving high-strength fence type composite anode plate for nonferrous metal electrodeposition according to claim 4, wherein: the height of the aluminum conductive beam (1) is 10-60 mm, the thickness is 10-40 mm, the thickness of the glass fiber cloth is 0.2-2 mm, the thickness of the lead-tin layer is 0.1-2 mm, and the diameter of the cooling liquid circulating channel is 0.5-10 mm.
6. The energy-saving high-strength fence type composite anode plate for the non-ferrous metal electrodeposition as claimed in claim 2, wherein: the inner layer copper bar (22) in the copper-aluminum composite conductive head (2) is of a heterogeneous structure, and the thickness is 5-20 mm; the aluminum cladding layer (21) comprises a tin transition layer and an aluminum surface layer, the thickness of the tin transition layer is 1-10 mu m, and the thickness of the aluminum surface layer is 5-30 mm.
7. The energy-saving high-strength fence type composite anode plate for the non-ferrous metal electrodeposition as claimed in claim 1, wherein: the thickness of the zinc layer in the transition layer (72) is 0.5-2 μm, the thickness of the copper layer is 3-8 μm, and the thickness of the lead-tin-rare earth composite layer is 4-20 μm; the mass percentage of tin in the lead-tin-rare earth composite layer is 5-30%, the mass percentage of rare earth is 0.01-0.5%, and the balance is lead.
8. The energy-saving high-strength fence type composite anode plate for nonferrous metal electrodeposition according to claim 1, wherein: the lead-bismuth-antimony/rare earth-nano cobalt composite layer (73) is calculated by the mass fraction of 100%, bismuth accounts for 0.01-1%, antimony accounts for 0.5-5%, rare earth accounts for 0.01-0.1%, nano cobalt accounts for 0.01-0.5%, and the balance of Pb.
9. The energy-saving high-strength fence type composite anode plate for the non-ferrous metal electrodeposition as claimed in claim 1, wherein: the surface of the Al-Ti-B particle is coated with a lead-silver composite coating (74), the granularity of the Al-Ti-B particle is 0.05-0.5 mm, and the thickness of the lead-silver composite coating is 0.1-0.6 mm; by taking the mass fraction of the lead-silver composite plating layer (74) coated on the surface of the aluminum-titanium-boron particles as 100%, 5-12% of lead, 0.5-3.0% of silver, 1-5% of titanium, 0.1-1% of boron and the balance of aluminum are contained in the aluminum-titanium-boron particles.
10. The preparation method of the energy-saving high-strength fence type composite anode plate for the non-ferrous metal electrodeposition as claimed in any one of claims 1 to 9 is characterized by comprising the following specific steps:
1) Sequentially carrying out alkali washing, deionized water washing, ultrasonic cleaning, acid activation treatment, deionized water washing, zinc dipping treatment, deionized water washing, pyrophosphate copper plating treatment, deionized water washing, methylsulfonate lead-tin rare earth alloy plating treatment, deionized water washing, lead-bismuth-antimony-rare earth nano cobalt powder plating treatment of a fluoboric acid system, deionized water washing, extrusion drawing composite rod treatment, acid washing for oil removal, deionized water washing and drying, spraying aluminum-titanium-boron composite particles with surfaces coated with lead and silver, carrying out heat treatment, taking up and carrying out fixed-length shearing on an aluminum wire to obtain an anode composite rod;
2) Welding a copper-aluminum composite conductive head and one end of an aluminum conductive beam, welding an anode composite rod on the bottom end of the aluminum conductive beam to form a fence-type aluminum-based composite anode plate support, horizontally die-casting multiple layers of conductive reinforcing ribs on the fence-type aluminum-based composite anode plate support, installing insulating sheaths on two sides of the fence-type aluminum-based composite anode plate support, and installing insulators on the fence-type aluminum-based composite anode plate support to obtain the energy-saving high-strength fence-type composite anode plate for non-ferrous metal electrodeposition.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116666648A (en) * | 2023-06-26 | 2023-08-29 | 昆明理工恒达科技股份有限公司 | Aluminum-based composite polar plate for high-capacity long-service-life lead-carbon energy storage battery and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116666648A (en) * | 2023-06-26 | 2023-08-29 | 昆明理工恒达科技股份有限公司 | Aluminum-based composite polar plate for high-capacity long-service-life lead-carbon energy storage battery and preparation method thereof |
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