CN113862759B - Titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and preparation method thereof - Google Patents
Titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and preparation method thereof Download PDFInfo
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- CN113862759B CN113862759B CN202111267586.4A CN202111267586A CN113862759B CN 113862759 B CN113862759 B CN 113862759B CN 202111267586 A CN202111267586 A CN 202111267586A CN 113862759 B CN113862759 B CN 113862759B
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- copper
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000010949 copper Substances 0.000 title claims abstract description 107
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 107
- 239000002131 composite material Substances 0.000 title claims abstract description 101
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 92
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000010936 titanium Substances 0.000 title claims abstract description 78
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 78
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000007772 electrode material Substances 0.000 title claims abstract description 36
- 239000011521 glass Substances 0.000 claims abstract description 89
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 74
- 239000010941 cobalt Substances 0.000 claims abstract description 74
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 48
- 229910006529 α-PbO Inorganic materials 0.000 claims abstract description 35
- 229910003134 ZrOx Inorganic materials 0.000 claims abstract description 33
- 230000007704 transition Effects 0.000 claims abstract description 31
- 239000004005 microsphere Substances 0.000 claims abstract description 17
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 133
- 239000011324 bead Substances 0.000 claims description 72
- 239000002245 particle Substances 0.000 claims description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 47
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 43
- 238000007747 plating Methods 0.000 claims description 41
- 239000011248 coating agent Substances 0.000 claims description 40
- 238000000576 coating method Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 238000009713 electroplating Methods 0.000 claims description 27
- 230000002378 acidificating effect Effects 0.000 claims description 22
- 239000011159 matrix material Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000005238 degreasing Methods 0.000 claims description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 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 claims description 9
- 238000005554 pickling Methods 0.000 claims description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- 101710134784 Agnoprotein Proteins 0.000 claims description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 7
- 101150003085 Pdcl gene Proteins 0.000 claims description 7
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 7
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 7
- 230000001235 sensitizing effect Effects 0.000 claims description 7
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 7
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
- 229940046892 lead acetate Drugs 0.000 claims description 6
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 238000005488 sandblasting Methods 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007788 roughening Methods 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 abstract description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 abstract description 2
- 239000011565 manganese chloride Substances 0.000 abstract description 2
- 235000002867 manganese chloride Nutrition 0.000 abstract description 2
- 229940099607 manganese chloride Drugs 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 13
- 238000010907 mechanical stirring Methods 0.000 description 13
- 230000001680 brushing effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 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 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 8
- 239000001119 stannous chloride Substances 0.000 description 8
- 235000011150 stannous chloride Nutrition 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 229910000978 Pb alloy Inorganic materials 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910003460 diamond Inorganic materials 0.000 description 6
- 239000010432 diamond Substances 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000008313 sensitization Effects 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
- 239000012459 cleaning agent Substances 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 4
- 229940038773 trisodium citrate Drugs 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical compound [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- -1 iron ion Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 238000005253 cladding Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 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 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910014474 Ca-Sn Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- SYZKBMPNHSQNHG-UHFFFAOYSA-N [Na].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN Chemical compound [Na].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN SYZKBMPNHSQNHG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to a titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and a preparation method thereof, belonging to the technical field of hydrometallurgical anode plates. The titanium-based gradient lead dioxide composite electrode material for copper electrodeposition sequentially comprises a titanium substrate, a Sn-Ru-Ta-ZrOx oxide bottom layer, a beta-PbO 2 -nano SnO 2 middle layer, an alpha-PbO 2 -copper coated graphite powder transition layer and a beta-PbO 2 -nano ZrN-cobalt coated hollow glass microsphere active layer from inside to outside. The invention also provides a preparation method of the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition. The electrode material provided by the invention is applied to electrodeposited copper, and compared with the traditional Pb-0.06wt% Ca-1.2wt% Sn anode, the electrode material can reduce 480mV, prolong the service life by more than 3 times, improve the current efficiency by more than 5 percent and improve the current density by more than 2 times in electrolytic copper solution containing no cobalt ions but containing manganese chloride ions.
Description
Technical Field
The invention relates to a titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and a preparation method thereof, belonging to the technical field of hydrometallurgical anode plates.
Background
At present, copper resource ores with lower ore grade account for more than half, along with the increasingly exploitation of high-grade copper ores by human beings, and the distribution of the copper ores has the characteristics of ore deposit dispersion, more points and less quantity, the pyrometallurgical copper smelting technology has high energy consumption, low yield and large environmental pollution, and the requirements of people production cannot be met, so that the application of the wet copper smelting technology with the advantages of treating oxidized ores and low-grade sulphide ores is increasingly wide.
The wet process for producing copper requires a large number of anodes of lead alloy material. At present, when copper is electrodeposited by a wet method, the current density is generally in the range of 200-260A/m < 2 >, the electrolysis period is 7-10 d, 3000-4000 anode plates are needed for producing 1 ten thousand t copper, a large number of electrolytic tanks and stainless steel cathode plates are also needed, the one-time investment is large, and the recovery period is long. Under the existing conditions, the current density is improved to be one of effective methods for improving the yield of the electrolytic copper. However, increasing the current density can polarize the concentration, resulting in an increase in cell voltage, and resulting in coarsening of the cathode copper particles, an increase in anode corrosion rate, and an increase in lead ion content in the solution. Therefore, when the current density is increased, it is necessary to increase the circulation speed of the electrolyte, to appropriately adjust the additives, to change the anode plate structure, and the like. In the use process of the traditional Pb-Ca-Sn anode plate, the flowing performance of electrolyte is poor, so that the quality of electrolytic copper cannot be further improved, and the production efficiency cannot be further improved. In addition, the conventional anode plate is used, manganese ions and chloride ions exist in the solution, corrosion is aggravated, and cobalt ions which are generally added into the electrolyte by 100-200 mg/L can form an activation center together with lead oxide, so that the overpotential of oxygen precipitation is reduced, firm oxide is formed, and lead-containing particles are reduced. But increase production costs and labor intensity.
In order to solve the environmental problems and the energy consumption problems caused by electrodeposited copper, higher performance anode substitutes have been developed. For example:
lead-based anode plate: efforts made by enterprises aiming at anode plate nodes are concentrated on adding elements such as silver, calcium, strontium, cobalt, rare earth and the like, and on the aspects of plate shape and plate shape rolling technology, the metal hardness and crystallization compactness of the lead alloy are increased, and although the lead alloy has an electricity-saving effect, the phenomena of poor conductivity, easy bending deformation, easy pollution to cathode products and the like of the lead alloy matrix are unavoidable.
Coating titanium anode: the anode is formed by coating a layer of noble metal oxide (such as RuO 2 or IrO 2) on the surface of a titanium electrode, and has the advantages of low energy consumption (10% -17%), capability of avoiding lead deposition in an electrowinning tank and pollution to a cathode product, and no need of adding cobalt sulfate; however, the main disadvantage of the anode is that the surface of the coating is covered by a layer of scale, which eventually increases the cell voltage, and the uniformity of the copper product is poor, resulting in anode failure, too short service life and too high material cost.
An anode is obtained by taking light metal aluminum as an inner core and mutually dissolving an outer layer lead alloy in a fusion casting or electroplating mode: the problems that the fluidity of lead alloy liquid is not solved and holes possibly appear in the part of the large-size anode plate are solved; secondly, a certain grain boundary gap can appear in the plating layer, oxygen generated during electrolysis permeates through the grain boundary gap alumina matrix of the plating layer to form an alumina film layer with poor conductivity, and the anode performance is deteriorated.
Fence type anode plate for nonferrous metal electrodeposition: the flow property of the electrolyte is improved, the effect and quality of collecting the electrolytic nonferrous metals are improved, and the defect that the anode plate is touched when the cathode plate is lifted is avoided. The low-cost aluminum bar is used as a matrix, so that the material cost is obviously reduced, but the defects of interface resistance, short service life, low strength and high tank voltage still exist.
The traditional anode beta-PbO 2 active layer has low adhesive force on a lead matrix and is easy to peel off, and a cathode product is easy to dye in the electrolysis process. alpha-PbO 2 is tightly combined with a lead matrix, but alpha-PbO 2 serving as an anode has low oxygen evolution overpotential, high porosity and poor corrosion resistance, cannot be independently used as an anode, can generate a coating without internal stress by adding particle composite electrodeposition, and has poor corrosion resistance as an outer layer, low cathode copper quality and short service life as the outer layer.
Disclosure of Invention
Aiming at the problem that the traditional titanium-based lead dioxide electrode is easy to passivate so as to influence the interface conductivity in the prior art, the invention provides a titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and a preparation method thereof, and the invention combines the pulse electrodeposition and composite plating technology when preparing a beta-PbO 2 -nano SnO 2 intermediate layer, wherein the pulse electrodeposition is used for the anodic oxidation/cathodic reduction of metal ions, the instantaneous high current density during the current conduction enables the metal ions to be oxidized/reduced under extremely high overpotential, and concentration polarization is effectively eliminated during the current turn-off period, thereby improving the deep plating capability of a plating solution, ensuring that the crystallization of the plating layer is fine and uniform, the porosity is low, the internal stress is small, even changing the preferred orientation of crystal faces to obtain nano crystal grains, and effectively improving the physical and chemical properties of the plating layer. The titanium-based gradient lead dioxide composite electrode material for copper electrodeposition has the advantages of good electrocatalytic activity, low cell voltage, low energy consumption, long service life, high electrolysis current density, high electrical efficiency and high strength.
The titanium-based gradient lead dioxide composite electrode material for copper electrodeposition sequentially comprises a titanium substrate, a Sn-Ru-Ta-ZrOx oxide bottom layer, a beta-PbO 2 -nano SnO 2 middle layer, an alpha-PbO 2 -copper coated graphite powder transition layer and a beta-PbO 2 -nano ZrN-cobalt coated hollow glass microsphere active layer from inside to outside.
Preferably, the molar ratio of the metals Sn, ru, ta and Zr in the underlying Sn-Ru-Ta-ZrOx oxide is (50-90): 1-10): 5-20): 4-20, respectively; the mass content of SnO 2 in the intermediate layer beta-PbO 2 -nano SnO 2 is 0.1-1.5 wt%; the mass content of the copper-clad graphite powder in the transition layer alpha-PbO 2 -copper-clad graphite powder is 1.0-3.2 wt%; the mass content of the nanometer ZrN particles in the active layer beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass bead is 0.6-1.8 wt%, and the content of the cobalt coated hollow glass bead is 0.5-5.0 wt%.
Preferably, the thickness of the Sn-Ru-Ta-ZrOx oxide bottom layer is 0.5-10 mu m, the thickness of the beta-PbO 2 -nano SnO 2 middle layer is 100-500 mu m, the thickness of the alpha-PbO 2 -copper coated graphite powder transition layer is 100-400 mu m, and the thickness of the beta-PbO 2 -nano ZrN-cobalt coated hollow glass bead active layer is 100-1200 mu m.
Preferably, the nano SnO 2 particles of the beta-PbO 2 -nano SnO 2 intermediate layer are spherical and have the particle size of 10-60 nm; the copper-coated graphite powder in the alpha-PbO 2 -copper-coated graphite powder transition layer is flaky, and the grain diameter is 1-20 mu m; the particle size of the nanometer ZrN particles in the beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass bead active layer is 20-80 nm, the particles of the cobalt coated hollow glass bead are round or elliptic, and the particle size is 0.1-1.0 mm.
Preferably, the titanium substrate is made of TA1 or TA2, the shape is net-shaped, the thickness is 0.5-4 mm, and silicon carbide sand or stainless steel shots are sprayed on the surface of the titanium substrate;
More preferably, the mesh-shaped hole pattern of the titanium matrix is diamond, square or round; the aperture of the diamond is (a.times.b) mm, wherein a is 1-5, b is 3-10, and a is less than b; the aperture of the square or round shape is 8-50 mm;
More preferably, the silicon carbide is green silicon carbide, has a spherical or hexagonal shape, has a particle size of 40-300 meshes, the stainless steel shot component is 316L, has a spherical shape, and has a particle size of 10-200 meshes.
The preparation method of the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition comprises the following specific steps:
(1) Sequentially carrying out sand blasting, oil removing and coarsening treatment on the titanium mesh to obtain a coarsened titanium mesh, cleaning the coarsened titanium mesh by deionized water, and then placing the coarsened titanium mesh in oxalic acid solution or absolute ethyl alcohol;
preferably, the deoiling cleaning agent is JC-300 or IC-518 diluent, the deoiling temperature is 40-60 ℃, and the deoiling time is 5-10 min; the roughening solution is HCl solution, the mass concentration of the HCl solution is 10-30%, and the roughening time is 0.5-3 h; the mass concentration of the oxalic acid solution is 1-3%;
(2) Preparation of Sn-Ru-Ta-ZrOx oxide underlayer: coating the coating liquid for 8-16 times on the roughened titanium mesh surface in the step (1), sequentially carrying out drying and sintering treatment after each coating, and carrying out heat treatment on the titanium mesh at 400-600 ℃ for 0.5-2 h after the coating liquid is coated for the last time to obtain a Sn-Ru-Ta-ZrOx oxide bottom layer on the titanium substrate surface; the coating liquid contains tin tetrachloride, ruthenium trichloride, tantalum pentachloride and zirconium nitrate, and the solvent of the coating liquid is a mixed liquid of concentrated hydrochloric acid and n-butanol;
preferably, the coating liquid contains 0.4 to 0.84mol/L of stannic chloride, 0.008 to 0.08mol/L of ruthenium trichloride, 0.04 to 0.16mol/L of tantalum pentachloride and 0.04 to 0.16mol/L of zirconium nitrate; the sintering temperature is 400-600 ℃, the sintering time is 5-10 min, and the total loading of the Sn-Ru-Ta-ZrOx oxide bottom layer is 5-20 g/m 2;
(3) Preparation of a beta-PbO 2 -nano SnO 2 intermediate layer: placing the titanium mesh obtained in the step (2) into an acidic composite electroplating solution, taking the titanium mesh as a cathode, and performing composite pulse electrodeposition for 0.5-3 h under stirring at the temperature of 40-80 ℃ to obtain a beta-PbO 2 -nano SnO 2 intermediate layer; wherein the acidic composite electroplating solution contains lead nitrate, cerium nitrate, bismuth nitrate and nano tin dioxide;
Preferably, the acidic composite plating solution contains 100-500 g/L of lead nitrate, 0.1-1 g/L of cerium nitrate, 0.1-2 g/L of bismuth nitrate, 1-50 g/L of HNO 3 and 2-20 g/L of nano tin dioxide; the positive duty ratio of the composite pulse electrodeposition is 10-50%, the negative duty ratio is 10-50%, the positive average current density is 3-8A/dm 2, and the negative average current density is 0.3-3A/dm 2;
(4) Preparation of an alpha-PbO 2 -copper-clad graphite powder transition layer: placing the titanium mesh obtained in the step (3) into alkaline composite electroplating solution, taking a stainless steel mesh as a cathode, and performing composite electrodeposition for 1-10 h under stirring at the temperature of 40-80 ℃ to obtain an alpha-PbO 2 -copper-clad graphite powder transition layer; wherein the alkaline composite electroplating solution contains lead acetate, sodium ethylenediamine tetraacetate, sodium hydroxide and copper-coated graphite powder;
Preferably, the alkaline composite plating solution contains 60-120 g/L of lead acetate, 10-50 g/L of sodium ethylenediamine tetraacetate, 100-200 g/L of sodium hydroxide and 5-30 g/L of copper-coated graphite powder; the current density of the composite electrodeposition is 0.2-3A/dm 2;
(5) Preparation of a beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass microsphere active layer: placing the titanium mesh obtained in the step (4) into an acidic composite electroplating solution, taking the titanium mesh as a cathode, and carrying out composite electrodeposition for 1-6 hours under stirring at the temperature of 40-80 ℃ to obtain a titanium-based gradient lead dioxide composite electrode material for copper electrodeposition, wherein the acidic composite electroplating solution contains lead methylsulfonate, methylsulfonic acid, nano ZrN and cobalt-coated hollow glass microspheres;
Preferably, the acidic composite plating solution contains 50-350 g/L of lead methylsulfonate, 30-200 g/L of methylsulfonic acid, 3-12 g/L of nano ZrN and 6-24 g/L of cobalt-coated hollow glass beads; the current density of the composite electrodeposition is 1-6A/dm 2.
The preparation method of the copper-coated graphite powder comprises the following specific steps:
(1) Sequentially degreasing the flake graphite powder by using a NaOH solution and pickling by using a HNO 3 solution to obtain pickled flake graphite powder;
Preferably, the concentration of the NaOH solution is 20-40%, and the oil removal time is 20-40 min; the concentration of HNO 3 solution is 10-30%, the pickling temperature is 25-50 ℃, and the pickling time is 10-20 min;
(2) Placing the acid-washed flake graphite powder into stannous chloride-hydrochloric acid solution, sensitizing for 5-10 min at the temperature of 25-60 ℃, and washing with deionized water until the powder is neutral to obtain sensitized flake graphite powder;
preferably, stannous chloride (SnCl 2·2H2 O) in the stannous chloride-hydrochloric acid solution is 10-30 g/L and hydrochloric acid solution is 10-30 mL/L;
(3) Placing the sensitized flaky graphite powder in PdCl 2 -hydrochloric acid solution for activation for 4-12 min, washing with deionized water to neutrality, and drying to obtain activated flaky graphite powder;
preferably, the PdCl 2 -hydrochloric acid solution contains 0.1-0.4 g/L of PdCl 2 and 10-20 ml/L of hydrochloric acid solution;
(4) Placing the activated flake graphite powder into an electroless copper plating solution, chemically plating for 30-120 min at 40-70 ℃ under stirring, washing with deionized water to be neutral, and vacuum drying to obtain copper-coated graphite powder; wherein the electroless copper plating solution contains copper sulfate, hydrazine hydrate, complexing agent and ammonia water;
Preferably, the complexing agent is sodium ethylenediamine tetraacetate or potassium sodium tartrate, the copper sulfate (CuSO 4·5H2 O) in the electroless copper plating solution is 5-40 g/L, hydrazine hydrate is 4-20 ml/L, complexing agent is 10-30 g/L, and ammonia water is 5-40 ml/L; the copper-coated graphite powder contains 5 to 30wt.% copper.
The preparation method of the cobalt-coated hollow glass microsphere comprises the following specific steps:
(1) Placing the hollow glass beads in NaOH-Na 2CO3 mixed solution for degreasing treatment for 10-30 min;
Preferably, 15-35 g/L, na 2CO3 -30 g/L NaOH in the NaOH-Na 2CO3 mixed solution;
(2) Placing the deoiled hollow glass beads in NH 4 F-HCl mixed solution, and coarsening for 3-10 min to obtain coarsened hollow glass beads;
Preferably, NH 4 F5-20 g/L, HCl-5 ml/L in NH 4 F-HCl mixed solution;
(3) The coarsened hollow glass beads are placed in stannous chloride-hydrochloric acid solution and sensitized for 5 to 10 minutes at the temperature of 25 to 60 ℃ to obtain sensitized hollow glass beads;
Preferably, stannous chloride (SnCl 2·2H2 O) in the stannous chloride-hydrochloric acid solution is 5-20 g/L and hydrochloric acid is 5-20 mL/L;
(4) The sensitized hollow glass beads are placed in AgNO 3 -ammonia water, and activated for 5-20 min to obtain activated hollow glass beads;
Preferably, agNO 3 in AgNO 3 -ammonia water is 0.5-3 g/L, and ammonia water is 5-20 mL/L;
(5) Placing the activated hollow glass beads in an electroless cobalt plating solution, carrying out electroless plating for 30-120 min under stirring at the temperature of 40-80 ℃, washing with deionized water to be neutral, and carrying out vacuum drying to obtain cobalt-coated hollow glass beads;
preferably, the electroless cobalt plating solution contains 0.1 to 0.4mol/L cobalt sulfate (CoSO 4·7H2 O), 0.2 to 0.5mol/L complexing agent, 0.2 to 0.4mol/L sodium hypophosphite and 40 to 200ml/L ammonia water; wherein the complexing agent is sodium ethylenediamine tetraacetate or trisodium citrate; the cobalt content of the cobalt-coated hollow glass beads is 5-20 wt.%.
The beneficial effects of the invention are as follows:
(1) The titanium-based gradient lead dioxide composite electrode for copper electrodeposition solves the problem that the traditional titanium-based lead dioxide electrode is easy to passivate under the conditions of strong acid and strong oxidizing property so as to influence the interface conductivity;
(2) The alpha-PbO 2 -copper-clad graphite powder transition layer can improve the binding force between the intermediate layer and the surface active layer, and alleviate the generation of electrodeposition distortion, thereby prolonging the service life of the titanium-based gradient lead dioxide electrode;
(3) According to the invention, the surface of the titanium screen plate is roughened before electrodepositing lead dioxide, and a layer of Sn-Ru-Ta-ZrOx oxide bottom layer with good conductivity and strong corrosion resistance is coated, so that the deposited beta-PbO 2 -nano SnO 2 middle layer is combined more tightly;
(4) The beta-PbO 2 -nano SnO 2 intermediate layer combines the pulse electrodeposition and the composite plating technology, and the target solid particles, the metal ions and the matrix metal are co-deposited to obtain composite plating layers with different performances meeting the requirements; the grains of the coating deposited by pulse electrodeposition are finer, so that electrolyte is prevented from penetrating into the bottom layer or the titanium base, and the service life of the electrode is greatly prolonged;
(5) The copper-clad graphite powder is doped into the alpha-PbO 2 coating, so that the conductivity of the alpha-PbO 2 is greatly improved, the conduction efficiency of the coating is improved, the resistance of the coating is reduced, and the cell voltage in the electrolysis process is reduced;
(6) According to the invention, the environment-friendly methylsulfonic acid electroplating solution is adopted to dope conductive nano ZrN particles and a cobalt-coated hollow glass bead composite electro-deposition beta-PbO 2 composite coating with catalytic activity, so that the electro-catalytic activity of the composite electrode is improved, the effect of energy conservation and consumption reduction can be achieved without adding cobalt ions when the electrode is applied to an electrodeposited copper solution, and the durability of the service life of the electrode is ensured;
(7) The titanium-based gradient lead dioxide composite electrode material is applied to electrodeposited copper, and compared with the traditional Pb-0.06wt% Ca-1.2wt% Sn anode, the titanium-based gradient lead dioxide composite electrode material can reduce 480mV, prolong the service life by 4 times, improve the current efficiency by more than 5 percent and improve the current density by more than 2 times in electrolytic copper solution without cobalt ions and containing manganese chloride ions.
Drawings
FIG. 1 is a schematic cross-sectional structure of a titanium-based gradient lead dioxide composite electrode material;
In the figure: 1-titanium matrix, 2-Sn-Ru-Ta-ZrOx oxide bottom layer, 3-beta-PbO 2 -nano SnO 2 middle layer, 4-alpha-PbO 2 -copper cladding graphite powder transition layer, 5-beta-PbO 2 -nano ZrN-cobalt cladding hollow glass microsphere active layer;
FIG. 2 is a surface topography of an underlying Sn-Ru-Ta-ZrOx oxide layer of example 1;
FIG. 3 is a surface morphology of the hollow glass beads of example 1;
FIG. 4 is a graph showing the surface energy spectrum of the cobalt-coated hollow glass microsphere of example 1.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
The titanium-based gradient lead dioxide composite electrode material for copper electrodeposition (see figure 1) comprises a titanium substrate 1, a Sn-Ru-Ta-ZrOx oxide bottom layer 2, a beta-PbO 2 -nano SnO 2 middle layer 3, an alpha-PbO 2 -copper coated graphite powder transition layer 4 and a beta-PbO 2 -nano ZrN-cobalt coated hollow glass bead active layer 5 from inside to outside in sequence;
The mol ratio of the metal Sn, ru, ta and Zr in the underlying Sn-Ru-Ta-ZrOx oxide is (50-90): 1-10): 5-20): 4-20 respectively; the mass content of SnO 2 in the intermediate layer beta-PbO 2 -nano SnO 2 is 0.1-1.5 wt%; the mass content of the copper-clad graphite powder in the transition layer alpha-PbO 2 -copper-clad graphite powder is 1.0-3.2 wt%; the mass content of the nanometer ZrN particles in the active layer beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass beads is 0.6-1.8 wt%, and the content of the cobalt coated hollow glass beads is 0.5-5.0 wt%;
The thickness of the Sn-Ru-Ta-ZrOx oxide bottom layer is 0.5-10 mu m, the thickness of the beta-PbO 2 -nano SnO 2 middle layer is 100-500 mu m, the thickness of the alpha-PbO 2 -copper coated graphite powder transition layer is 100-400 mu m, and the thickness of the beta-PbO 2 -nano ZrN-cobalt coated hollow glass bead active layer is 100-1200 mu m;
The nano SnO 2 particles of the beta-PbO 2 -nano SnO 2 intermediate layer are spherical and have the particle size of 10-60 nm; the copper-coated graphite powder in the alpha-PbO 2 -copper-coated graphite powder transition layer is flaky, and the grain diameter is 1-20 mu m; the particle size of the nanometer ZrN particles in the beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass bead active layer is 20-80 nm, the particles of the cobalt coated hollow glass bead are round or elliptical, and the particle size is 0.1-1.0 mm;
the titanium matrix is made of TA1 or TA2, the shape is net-shaped, the thickness is 0.5-4 mm, and silicon carbide sand or stainless steel shots are sprayed on the surface of the titanium matrix;
The reticular hole pattern of the titanium matrix is diamond, square or round; the aperture of the diamond is (a.times.b) mm, wherein a is 1-5, b is 3-10, and a is less than b; the aperture of the square or round shape is 8-50 mm;
the silicon carbide is green silicon carbide, the shape is spherical or hexagonal, the grain size is 40-300 meshes, the stainless steel shot component is 316L, the grain size is 10-200 meshes.
Example 1: in the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition, the molar ratio of metal Sn, ru, ta and Zr in the underlying Sn-Ru-Ta-ZrOx oxide is 70:5:12:13 respectively; the mass content of SnO 2 in the intermediate layer beta-PbO 2 -nano SnO 2 is 1.0wt.%; 2.2wt.% of copper-clad graphite powder in the transition layer alpha-PbO 2 -copper-clad graphite powder; the mass content of the nanometer ZrN particles in the active layer beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass beads is 1.2 wt%, and the content of the cobalt coated hollow glass beads is 2.0 wt%;
The thickness of the Sn-Ru-Ta-ZrOx oxide bottom layer is 4 mu m, the thickness of the beta-PbO 2 -nano SnO 2 middle layer is 200 mu m, the thickness of the alpha-PbO 2 -copper coated graphite powder transition layer is 300 mu m, and the thickness of the beta-PbO 2 -nano ZrN-cobalt coated hollow glass bead active layer is 600 mu m;
The nano SnO 2 particles of the intermediate layer of the beta-PbO 2 -nano SnO 2 are spherical, the particle size is 30nm, the copper-coated graphite powder in the transition layer of the alpha-PbO 2 -copper-coated graphite powder is flake-shaped, the particle size is 10 mu m, the particle size of the nano ZrN particles in the active layer of the beta-PbO 2 -nano ZrN-cobalt-coated hollow glass bead is 40nm, the particles of the cobalt-coated hollow glass bead are round or elliptic, and the particle size is 0.2mm;
The titanium matrix is made of TA1, the surface of the titanium matrix is sprayed with green silicon carbide, the titanium matrix is hexagonal, the particle size is 100 meshes, the titanium appearance is netlike, the hole pattern is diamond, the aperture of the diamond is 3X 5mm, and the thickness of the net is 2mm;
The preparation method of the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition comprises the following specific steps:
(1) Titanium-based pretreatment: performing sand blasting treatment on the titanium mesh, then placing the titanium mesh in a cleaning agent JC-300 diluent, removing oil for 8min at 50 ℃, and immediately washing the titanium mesh with water; then placing the mixture into an HCl solution with the concentration of 25%, coarsening the mixture for 2 hours at the temperature of 90 ℃, washing the mixture with deionized water, and immediately placing the mixture into a 1% oxalic acid solution for storage;
(2) Preparation of Sn-Ru-Ta-ZrOx oxide underlayer: after the titanium mesh treated in the step (1) is dried, brushing a coating solution on the surface of the titanium mesh, wherein the coating solution contains 0.60mol/L tin tetrachloride, 0.02mol/L ruthenium trichloride, 0.10mol/L tantalum pentachloride and 0.08mol/L zirconium nitrate, the solvent of the coating solution is a mixed solution of 10% concentrated hydrochloric acid and 90% n-butanol by volume, and the coating solution is obtained by filtering through 1PS filter paper after the preparation of the coating solution; drying the titanium mesh at 100 ℃ for 8min after each brushing, then sintering the titanium mesh at 500 ℃ for 8min in a muffle furnace, cooling the titanium mesh to room temperature, repeating the coating for 10 times, and finally brushing and drying the titanium mesh sequentially and then performing heat treatment at 500 ℃ for 1h to obtain a Sn-Ru-Ta-ZrOx oxide bottom layer, wherein the total loading amount is 12g/m 2 as shown in figure 2;
(3) Preparation of a beta-PbO 2 -nano SnO 2 intermediate layer: placing the titanium base obtained in the step (2) into an acidic composite electroplating solution, taking a titanium mesh as a cathode, and carrying out composite pulse electrodeposition for 2 hours at the temperature of 60 ℃ and the rotating speed of 200rpm by adopting mechanical stirring; wherein the positive duty cycle of the composite pulse electrodeposition is 20%, the negative duty cycle is 20%, the positive average current density is 5A/dm 2, and the negative average current density is 0.5A/dm 2; the acidic composite plating solution contains 200g/L of lead nitrate (Pb (NO 3)2), 0.3g/L of cerium nitrate (Ce (NO 3)3), and 10g/L of bismuth nitrate (Bi (NO 3)3)0.5g/L、HNO3, 20g/L and nano tin dioxide (SnO 2);
(4) Preparation of an alpha-PbO 2 -copper-clad graphite powder transition layer: placing the titanium mesh obtained in the step (3) into an alkaline composite electroplating solution, taking a stainless steel mesh as a cathode, and performing composite electrodeposition for 4 hours at a temperature of 50 ℃ and a current density of 1A/dm 2 by adopting mechanical stirring at a rotating speed of 200 rpm; wherein the alkaline composite electroplating solution contains 100g/L of lead acetate (Pb (CH 3COO)2), 30g/L of sodium ethylenediamine tetraacetate, 160g/L of sodium hydroxide and 20g/L of copper-coated graphite powder;
(5) Preparation of a beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass microsphere active layer: placing the titanium mesh obtained in the step (4) into an acidic composite electroplating solution, taking the titanium mesh as a cathode, and performing composite electrodeposition for 2 hours at a temperature of 60 ℃ and a current density of 3A/dm 2 by adopting mechanical stirring at a rotating speed of 400 rpm; wherein the acidic composite plating solution contains 250g/L of lead methylsulfonate, 100g/L of methylsulfonic acid, 8g/L of nano ZrN and 12g/L of cobalt-coated hollow glass beads;
The preparation method of the copper-coated graphite powder comprises the following specific steps:
(1) Sequentially degreasing the flake graphite powder by using a NaOH solution and pickling by using a HNO 3 solution to obtain pickled flake graphite powder; wherein the concentration of NaOH solution is 20%, the oil removal temperature is 80 ℃, and the oil removal time is 30min; the concentration of HNO 3 solution is 20%, the pickling temperature is 40 ℃, and the pickling time is 12min;
(2) Placing the acid-washed flake graphite powder into stannous chloride-hydrochloric acid solution, sensitizing for 8min at the temperature of 40 ℃, and washing with deionized water until the powder is neutral to obtain sensitized flake graphite powder; wherein, stannous chloride (SnCl 2·2H2 O) in the stannous chloride-hydrochloric acid solution is 20g/L and hydrochloric acid solution is 20mL/L;
(3) Placing the sensitized flaky graphite powder in PdCl 2 -hydrochloric acid solution for activation for 8min, washing with deionized water to be neutral, and drying to obtain activated flaky graphite powder; wherein, the PdCl 2 -hydrochloric acid solution contains 0.3g/L of PdCl 2 and 12ml/L of hydrochloric acid solution;
(4) Placing the activated flake graphite powder into an electroless copper plating solution, chemically plating for 30-120 min at the temperature of 60 ℃ under stirring, washing with deionized water to be neutral, and vacuum drying to obtain copper-coated graphite powder; wherein, the copper sulfate (CuSO 4·5H2 O) in the electroless copper plating solution is 25g/L, hydrazine hydrate is 10ml/L, complexing agent is 20g/L and ammonia water is 20ml/L; copper content in the copper-clad graphite powder is 20wt.%; the complexing agent is sodium ethylenediamine tetraacetate;
the preparation method of the cobalt-coated hollow glass microsphere comprises the following specific steps:
(1) Placing the hollow glass beads in NaOH-Na 2CO3 mixed solution for degreasing treatment for 20min; wherein, naOH in the NaOH-Na 2CO3 mixed solution is 20g/L, na 2CO3 g/L;
(2) Placing the deoiled hollow glass beads in NH 4 F-HCl mixed solution, and coarsening for 6min to obtain coarsened hollow glass beads; wherein, NH 4 F10 g/L, HCl ml/L in NH 4 F-HCl mixed solution;
(3) The coarsened hollow glass beads are placed in stannous chloride-hydrochloric acid solution and sensitized at 40 ℃ for 5-10 min to obtain sensitized hollow glass beads; wherein, stannous chloride (SnCl 2·2H2 O) 10g/L and hydrochloric acid 10mL/L in the stannous chloride-hydrochloric acid solution;
(4) The sensitized hollow glass beads are placed in AgNO 3 -ammonia water, and activated for 10min to obtain activated hollow glass beads; wherein AgNO 3 g/L and ammonia water 10mL/L in AgNO 3 -ammonia water;
(5) Placing the activated hollow glass beads in an electroless cobalt plating solution, carrying out electroless plating for 90min at the temperature of 60 ℃ under stirring, washing with deionized water to be neutral, and carrying out vacuum drying to obtain cobalt-coated hollow glass beads; wherein the electroless cobalt plating solution contains 0.2mol/L cobalt sulfate (CoSO 4·7H2 O), 0.3mol/L trisodium citrate, 0.3mol/L sodium hypophosphite and 100ml/L ammonia water; the cobalt content of the cobalt-coated hollow glass beads is 10wt.%;
the surface morphology of the hollow glass bead is shown in figure 3, and the surface energy spectrum of the cobalt-coated hollow glass bead is shown in figure 4;
The titanium-based gradient lead dioxide composite electrode material for copper electrodeposition prepared in the embodiment is in copper electrolyte, the electrolysis condition is that the electrolyte copper ion concentration is 50g/L, the sulfuric acid concentration is 180g/L, the electrolyte temperature is 50 ℃, the iron ion concentration is 1g/L, the Cl - ion concentration is 100mg/L, the manganese ion concentration is 50mg/L, the current density is 300A/m 2, compared with the traditional Pb-0.06wt% Ca-1.2wt% Sn anode, the cell voltage of the titanium-based gradient lead dioxide composite electrode is reduced by 480mV, the service life is prolonged by 6 times, and the current efficiency is improved by 6%.
Example 2: in the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition, the molar ratio of metal Sn, ru, ta and Zr in the underlying Sn-Ru-Ta-ZrOx oxide is 50:10:20:20 respectively; 0.1wt.% of SnO 2 in the intermediate layer β -PbO 2 -nano SnO 2; 1.0wt.% of copper-clad graphite powder in the transition layer alpha-PbO 2 -copper-clad graphite powder; the mass content of the nanometer ZrN particles in the active layer beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass beads is 0.6wt.%, and the content of the cobalt coated hollow glass beads is 0.5wt.%;
The thickness of the Sn-Ru-Ta-ZrOx oxide bottom layer is 0.5 mu m, the thickness of the beta-PbO 2 -nano SnO 2 middle layer is 100 mu m, the thickness of the alpha-PbO 2 -copper coated graphite powder transition layer is 100 mu m, and the thickness of the beta-PbO 2 -nano ZrN-cobalt coated hollow glass bead active layer is 100 mu m;
The nano SnO 2 particles of the intermediate layer of the beta-PbO 2 -nano SnO 2 are spherical, the particle size is 10nm, the copper-coated graphite powder in the transition layer of the alpha-PbO 2 -copper-coated graphite powder is flake-shaped, the particle size is 1 mu m, the particle size of the nano ZrN particles in the active layer of the beta-PbO 2 -nano ZrN-cobalt-coated hollow glass bead is 20nm, the particles of the cobalt-coated hollow glass bead are round or elliptical, and the particle size is 0.1mm;
The titanium matrix is made of TA2, 316L stainless steel shots are sprayed on the surface of the titanium matrix, the titanium matrix is spherical, the particle size is 40 meshes, the titanium appearance is netlike, the hole pattern is square, the diagonal line length of the hole is 8mm, and the thickness of the net is 1mm;
The preparation method of the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition comprises the following specific steps:
(1) Titanium-based pretreatment: performing sand blasting treatment on the titanium mesh, then placing the titanium mesh into a cleaning agent IC-518 diluent, removing oil for 5min at the temperature of 40 ℃, and immediately washing the titanium mesh with water; then placing the titanium mesh into an HCl solution with the concentration of 10 percent, coarsening the titanium mesh at the temperature of 80 ℃ for 0.5h to obtain a coarsened titanium mesh, washing the titanium mesh with deionized water, and immediately placing the titanium mesh into absolute ethyl alcohol for storage;
(2) Preparation of Sn-Ru-Ta-ZrOx oxide underlayer: drying the coarsened titanium mesh in the step (1), brushing a coating solution on the surface of the titanium mesh, wherein the coating solution contains 0.24mol/L tin tetrachloride, 0.08mol/L ruthenium trichloride, 0.16mol/L tantalum pentachloride and 0.16mol/L zirconium nitrate, the solvent of the coating solution is a mixed solution of concentrated hydrochloric acid with the volume of 20% and n-butyl alcohol with the volume of 80%, filtering the coating solution through 1PS filter paper before brushing, drying the titanium mesh at the temperature of 80 ℃ for 5min after each brushing, then sintering the titanium mesh in a muffle furnace for 5min at the temperature of 400 ℃, cooling to room temperature, repeatedly coating for 8 times, brushing and drying the last time, and then performing heat treatment for 0.5h at the temperature of 400 ℃ to obtain a Sn-Ru-Ta-ZrOx oxide bottom layer, wherein the total loading amount of the Sn-Ru-Ta-ZrOx oxide bottom layer is 8g/m 2;
(3) Preparation of a beta-PbO 2 -nano SnO 2 intermediate layer: placing the titanium base obtained in the step (2) in an acidic composite electroplating solution, taking a titanium mesh as a cathode, and carrying out composite pulse electrodeposition for 0.5h under the mechanical stirring at the temperature of 40 ℃ and the rotating speed of 100rpm, wherein the positive duty ratio is 10%, the negative duty ratio is 10%, the positive average current density is 3A/dm 2, the negative average current density is 0.3A/dm 2, and the acidic composite electroplating solution comprises 100g/L of lead nitrate (Pb (NO 3)2), 0.1g/L of cerium nitrate (Ce (NO 3)3), and 2g/L of bismuth nitrate (Bi (NO 3)3)0.1g/L、HNO3 g/L and nano tin dioxide (SnO 2);
(4) Preparation of an alpha-PbO 2 -copper-clad graphite powder transition layer: placing the titanium mesh obtained in the step (3) in an alkaline composite electroplating solution, taking a stainless steel mesh as a cathode, and carrying out composite electrodeposition for 1h under the mechanical stirring of the current density of 0.2A/dm 2 and the rotating speed of 100rpm at the temperature of 40 ℃, wherein the alkaline composite electroplating solution contains 60g/L of lead acetate (Pb (CH 3COO)2), 20g/L of sodium ethylenediamine tetraacetate, 140g/L of sodium hydroxide and 5g/L of copper-coated graphite powder;
(5) Preparation of a beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass microsphere active layer: placing the titanium mesh obtained in the step (4) in an acidic composite electroplating solution, taking the titanium mesh as a cathode, and carrying out composite electrodeposition for 1h under the mechanical stirring with the temperature of 40 ℃ and the current density of 1A/dm 2 and the rotating speed of 200rpm, wherein the acidic composite electroplating solution contains 100g/L of lead methylsulfonate, 50g/L of methylsulfonic acid, 3g/L of nano ZrN and 6g/L of cobalt-coated hollow glass beads;
The copper-coated graphite powder is prepared by the following steps:
Firstly, placing flake graphite powder into a NaOH solution with the concentration of 20%, removing oil for 20min at the temperature of above 80 ℃, and washing with deionized water; then placing the mixture in HNO 3 solution with the concentration of 10 percent, and pickling for 10 minutes at the temperature of 25 ℃; then placing the mixture in a sensitization solution, sensitizing the mixture for 5 minutes at the temperature of 25 ℃, and washing the mixture with deionized water until the mixture is neutral, wherein the sensitization solution contains 10g/L stannous chloride (SnCl 2·2H2 O) and 10mL/L hydrochloric acid; then placing the mixture in an activating solution for activation for 4min, wherein the activating solution contains 0.1g/LPdCl 2 and 10ml/L hydrochloric acid; washing deionized water to be neutral, then placing the solution in a blast furnace drying box, drying the solution for 0.5h at the temperature of 80 ℃, placing the treated flaky graphite powder in an electroless copper plating solution, chemically plating the solution for 30min under the mechanical stirring at the temperature of 40 ℃ and the rotating speed of 100rpm, wherein the electroless copper plating solution contains 15g/L copper sulfate (CuSO 4·5H2 O), 4ml/L hydrazine hydrate, 10g/L potassium sodium tartrate and 5ml/L ammonia water, washing the solution to be neutral by adopting deionized water, carrying out suction filtration, and carrying out vacuum drying to obtain copper-coated graphite powder with copper content of 5 wt%;
the cobalt-coated hollow glass microsphere is prepared according to the following steps:
Placing the hollow glass beads into a mixed solution of 15g/LNaOH+10g/LNa 2CO3 for degreasing for 10min, and washing with deionized water for neutrality; coarsening in 5g/LNH 4 F+1ml/LHCl mixed solution for 3min, and washing with deionized water for neutral; putting into a sensitization solution containing 5g/L stannous chloride (SnCl 2·2H2 O) and 5mL/L hydrochloric acid, sensitizing for 5min at 25 ℃, and flushing with hot water to be neutral; then placing the solution in 0.5g/LAgNO 3 +5mL/L ammonia water for normal temperature activation for 5min, washing with deionized water for neutrality, immediately placing the solution in an electroless cobalt plating solution, carrying out electroless plating for 30min under mechanical stirring at 40 ℃ and 100rpm, wherein the electroless cobalt plating solution contains 0.1mol/L cobalt sulfate (CoSO 4·7H2 O), 0.2mol/L trisodium citrate, 0.2mol/L sodium hypophosphite and 40mL/L ammonia water, washing with deionized water to neutrality, carrying out suction filtration, and carrying out vacuum drying to obtain cobalt-coated hollow glass microspheres with copper content of 5 wt.%.
The titanium-based gradient lead dioxide composite electrode material for copper electrodeposition prepared in the embodiment is in copper electrolyte, the electrolysis condition is that the concentration of electrolyte copper ions is 50g/L, the concentration of sulfuric acid is 180g/L, the temperature of the electrolyte is 50 ℃, the iron ions are 1g/L, cl - ions are 100mg/L, the manganese ions are 50mg/L, the current density is 400A/m 2, compared with the traditional Pb-0.06wt% Ca-1.2wt% Sn anode, the cell voltage of the titanium-based gradient lead dioxide composite electrode is reduced by 280mV, the service life is prolonged by 3 times, and the current efficiency is improved by 4%.
Example 3: in the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition, the molar ratio of metal Sn, ru, ta and Zr in the underlying Sn-Ru-Ta-ZrOx oxide is 90:1:5:4 respectively; the mass content of SnO 2 in the intermediate layer beta-PbO 2 -nano SnO 2 is 1.5wt.%; 3.2wt.% of copper-clad graphite powder in the transition layer alpha-PbO 2 -copper-clad graphite powder; the mass content of the nanometer ZrN particles in the active layer beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass beads is 1.8 wt%, and the content of the cobalt coated hollow glass beads is 5.0 wt%;
The thickness of the Sn-Ru-Ta-ZrOx oxide bottom layer is 8 mu m, the thickness of the beta-PbO 2 -nano SnO 2 middle layer is 500 mu m, the thickness of the alpha-PbO 2 -copper coated graphite powder transition layer is 400 mu m, and the thickness of the beta-PbO 2 -nano ZrN-cobalt coated hollow glass bead active layer is 1000 mu m;
The nano SnO 2 particles of the intermediate layer of the beta-PbO 2 -nano SnO 2 are spherical, the particle size is 60nm, the copper-coated graphite powder in the transition layer of the alpha-PbO 2 -copper-coated graphite powder is flaky, the particle size is 20 mu m, the particle size of the nano ZrN particles in the active layer of the beta-PbO 2 -nano ZrN-cobalt-coated hollow glass bead is 80nm, the particles of the cobalt-coated hollow glass bead are round or elliptical, and the particle size is 1.0mm;
The titanium matrix is made of TA1, silicon carbide sand is sprayed on the surface of the titanium matrix, the titanium matrix is spherical, the particle size is 300 meshes, the titanium appearance is netlike, the hole pattern is circular, the diagonal line length of the hole is 50mm, and the thickness of the net is 4mm;
The preparation method of the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition comprises the following steps:
(1) Titanium-based pretreatment: firstly, carrying out sand blasting treatment on a titanium mesh, then putting the titanium mesh into a cleaning agent JC-300 diluent, degreasing for 10min at the temperature of 60 ℃, and immediately washing the titanium mesh with water; then placing the titanium mesh into a solution with the concentration of 30% HCl, coarsening the titanium mesh at the temperature of 100 ℃ for 3 hours to obtain a coarsened titanium mesh, washing the titanium mesh with deionized water, and immediately placing the titanium mesh into absolute ethyl alcohol for storage;
(2) Preparation of Sn-Ru-Ta-ZrOx oxide underlayer: drying the coarsened titanium mesh in the step (1), brushing a coating solution on the surface of the titanium mesh, wherein the coating solution contains 0.75mol/L tin tetrachloride, 0.008mol/L ruthenium trichloride, 0.04mol/L tantalum pentachloride and 0.04mol/L zirconium nitrate, the solvent of the coating solution is mixed solution of 10% concentrated hydrochloric acid and 90% n-butyl alcohol by volume, filtering the coating solution through 1PS filter paper before brushing, drying the titanium mesh at 120 ℃ for 10min after each brushing, then sintering the titanium mesh in a muffle furnace for 10min at 600 ℃, cooling the titanium mesh to room temperature, repeatedly coating for 16 times, and carrying out heat treatment for 2h at 600 ℃ after the last brushing and drying to obtain a Sn-Ru-Ta-ZrOx oxide bottom layer, wherein the total loading of the Sn-Ru-Ta-ZrOx oxide bottom layer is 20g/m 2;
(3) Preparation of a beta-PbO 2 -nano SnO 2 intermediate layer: placing the titanium base obtained in the step (2) in an acidic composite electroplating solution, taking a titanium mesh as a cathode, and carrying out composite pulse electrodeposition for 3 hours under the mechanical stirring at the temperature of 80 ℃ and the rotating speed of 500rpm, wherein the positive duty ratio is 30%, the negative duty ratio is 30%, the positive average current density is 8A/dm 2, and the negative average current density is 3A/dm 2; the acidic composite plating solution contains 400g/L of lead nitrate (Pb (NO 3)2), 1g/L of cerium nitrate (Ce (NO 3)3), 20g/L of bismuth nitrate (Bi (NO 3)3)2g/L、HNO3, 50g/L and nano tin dioxide (SnO 2);
(4) Preparation of an alpha-PbO 2 -copper-clad graphite powder transition layer: placing the titanium mesh obtained in the step (3) in an alkaline composite electroplating solution, taking a stainless steel mesh as a cathode, and carrying out composite electrodeposition for 10 hours under the mechanical stirring with the temperature of 80 ℃ and the current density of 2A/dm 2 and the rotating speed of 800rpm, wherein the alkaline composite electroplating solution contains 120g/L of lead acetate (Pb (CH 3COO)2), 50g/L of sodium ethylenediamine tetraacetate, 200g/L of sodium hydroxide and 30g/L of copper-coated graphite powder;
(5) Preparation of a beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass microsphere active layer: placing the titanium mesh obtained in the step (4) in an acidic composite electroplating solution, taking the titanium mesh as a cathode, and carrying out composite electrodeposition for 5 hours under the mechanical stirring of the temperature of 80 ℃ and the current density of 5A/dm 2 and the rotating speed of 800rpm, wherein the acidic composite electroplating solution contains 350g/L of lead methylsulfonate, 200g/L of methylsulfonic acid, 12g/L of nano ZrN and 24g/L of cobalt-coated hollow glass beads;
The copper-coated graphite powder is prepared by the following steps:
Firstly placing flake graphite powder into a NaOH solution with the concentration of 20%, degreasing for 40min at the temperature of more than 80 ℃, washing cleanly with deionized water, then placing into a HNO 3 solution with the concentration of 30%, pickling for 20min at the temperature of 50 ℃, placing into a sensitization solution containing 30g/L stannous chloride (SnCl 2·2H2 O) and 30mL/L hydrochloric acid, sensitizing for 10min at the temperature of 60 ℃, washing to neutrality with deionized water, placing into an activation solution containing 0.2g/LPdCl 2 and 10mL/L hydrochloric acid, activating for 12min, washing to neutrality with deionized water, placing into a blast furnace drying box, drying for 2h at the temperature of 200 ℃, placing the treated flake graphite powder into an electroless copper plating solution, chemically plating for 120min under mechanical stirring at the temperature of 70 ℃ and 400rpm, wherein the electroless copper plating solution contains 40g/L copper sulfate (CuSO 4·5H2 O), 20mL hydrazine hydrate, 30g/L ethylenediamine tetraacetic acid sodium and 40mL/L ammonia water, washing with deionized water to neutrality, and vacuum drying to obtain copper-containing 30wt.% graphite powder;
the cobalt-coated hollow glass microsphere is prepared according to the following steps:
Placing the hollow glass beads into 35g/LNaOH+30g/LNa 2CO3 mixed solution for degreasing for 10min, washing with deionized water for neutrality, then placing into 20g/LNH 4 F+5ml/LHCl mixed solution for coarsening for 10min, washing with deionized water for neutrality, then placing into sensitizing solution with the concentration of 20g/L stannous chloride (SnCl 2·2H2 O) and 20mL/L hydrochloric acid for sensitization for 10min at the temperature of 60 ℃, washing with hot water to neutrality, then placing into 3g/LAgNO 3 +20ml/L ammonia water for normal temperature activation for 20min, washing with deionized water for neutrality, immediately placing into electroless cobalt solution for electroless plating for 120min under mechanical stirring at the temperature of 80 ℃ and the rotation speed of 400rpm, wherein the electroless cobalt solution contains 0.4mol/L cobalt sulfate (CoSO 4·7H2 O), 0.5mol/L trisodium citrate, 0.4mol/L sodium hypophosphite and 200mL/L ammonia water, then washing with deionized water to neutrality for suction filtration, and vacuum drying to obtain copper-containing 20wt.% cobalt coated hollow glass beads;
The electrolytic condition of the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition prepared in the embodiment is that the electrolyte copper ion concentration is 50g/L, the sulfuric acid concentration is 180g/L, the electrolyte temperature is 50 ℃, the iron ion concentration is 1g/L, the Cl - ion concentration is 100mg/L, the manganese ion concentration is 50mg/L, the current density is 500A/m 2, compared with the traditional Pb-0.06wt% Ca-1.2wt% Sn anode, the cell voltage of the titanium-based gradient lead dioxide composite electrode is reduced by 420mV, the service life is prolonged by 4 times, and the current efficiency is improved by 3%.
While the present invention has been described in detail with reference to the drawings, the present invention is not limited to the above embodiments, 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 (9)
1. The preparation method of the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition is characterized by comprising the following specific steps:
(1) Sequentially carrying out sand blasting, oil removing and coarsening treatment on the titanium mesh to obtain a coarsened titanium mesh, cleaning the coarsened titanium mesh by deionized water, and then placing the coarsened titanium mesh in oxalic acid solution or absolute ethyl alcohol;
(2) Preparation of Sn-Ru-Ta-ZrOx oxide underlayer: coating the coating liquid on the surface of the coarsened titanium mesh in the step (1) for 8-16 times, sequentially carrying out drying and sintering treatment after each coating, and carrying out heat treatment on the titanium mesh at 400-600 ℃ for 0.5-2 h after the last coating liquid coating to obtain a Sn-Ru-Ta-ZrOx oxide bottom layer on the surface of the titanium substrate; the coating liquid contains tin tetrachloride, ruthenium trichloride, tantalum pentachloride and zirconium nitrate, and the solvent of the coating liquid is a mixed liquid of concentrated hydrochloric acid and n-butanol;
(3) Preparation of a beta-PbO 2 -nano SnO 2 intermediate layer: placing the titanium mesh obtained in the step (2) into an acidic composite electroplating solution, taking the titanium mesh as a cathode, and performing composite pulse electrodeposition for 0.5-3 hours under stirring at the temperature of 40-80 ℃ to obtain a beta-PbO 2 -nano SnO 2 intermediate layer; wherein the acidic composite plating solution contains 100-500 g/L of lead nitrate, 0.1-1 g/L of cerium nitrate, 0.1-2 g/L of bismuth nitrate, 1-50 g/L of HNO 3 and 2-20 g/L of nano tin dioxide; the positive duty ratio of the composite pulse electrodeposition is 10-50%, the negative duty ratio is 10-50%, the positive average current density is 3-8A/dm 2, and the negative average current density is 0.3-3A/dm 2;
(4) Preparation of an alpha-PbO 2 -copper-clad graphite powder transition layer: placing the titanium mesh obtained in the step (3) into alkaline composite electroplating solution, taking a stainless steel mesh as a cathode, and performing composite electrodeposition for 1-10 hours at the temperature of 40-80 ℃ under stirring to obtain an alpha-PbO 2 -copper-clad graphite powder transition layer; wherein the alkaline composite plating solution contains 60-120 g/L of lead acetate, 10-50 g/L of sodium ethylenediamine tetraacetate, 100-200 g/L of sodium hydroxide and 5-30 g/L of copper-coated graphite powder; the current density of the composite electrodeposition is 0.2-3A/dm 2;
(5) Preparation of a beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass microsphere active layer: placing the titanium mesh obtained in the step (4) into an acidic composite electroplating solution, and carrying out composite electrodeposition for 1-6 hours at the temperature of 40-80 ℃ by taking the titanium mesh as a cathode under stirring to obtain a titanium-based gradient lead dioxide composite electrode material for copper electrodeposition, wherein the acidic composite electroplating solution contains 50-350 g/L of lead methylsulfonate, 30-200 g/L of methylsulfonic acid, 3-12 g/L of nano ZrN and 6-24 g/L of cobalt-coated hollow glass beads; the current density of the composite electrodeposition is 1-6A/dm 2.
2. The method for preparing the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition according to claim 1, wherein the method comprises the following steps: in the step (1), the oil removal temperature is 40-60 ℃ and the oil removal time is 5-10 min; the roughening solution is an HCl solution, the mass concentration of the HCl solution is 10-30%, and the roughening time is 0.5-3 h; the mass concentration of the oxalic acid solution is 1-3%;
or/and the coating liquid in the step (2) contains 0.4-0.84 mol/L tin tetrachloride, 0.008-0.08 mol/L ruthenium trichloride, 0.04-0.16 mol/L tantalum pentachloride and 0.04-0.16 mol/L zirconium nitrate; the sintering temperature is 400-600 ℃, the sintering time is 5-10 min, and the total loading of the Sn-Ru-Ta-ZrOx oxide bottom layer is 5-20 g/m 2.
3. The method for preparing the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition according to claim 1, wherein the method comprises the following steps: the preparation method of the copper-coated graphite powder comprises the following specific steps:
(1) Sequentially degreasing the flake graphite powder by using a NaOH solution and pickling by using a HNO 3 solution to obtain pickled flake graphite powder;
(2) Placing the acid-washed flake graphite powder into stannous chloride-hydrochloric acid solution, sensitizing for 5-10 min at the temperature of 25-60 ℃, and washing with deionized water until the acid-washed flake graphite powder is neutral to obtain sensitized flake graphite powder;
(3) Placing the sensitized flaky graphite powder in PdCl 2 -hydrochloric acid solution for activation for 4-12 min, washing with deionized water to be neutral, and drying to obtain activated flaky graphite powder;
(4) Placing the activated flake graphite powder into an electroless copper plating solution, chemically plating for 30-120 min at the temperature of 40-70 ℃ under stirring, washing with deionized water to be neutral, and vacuum drying to obtain copper-coated graphite powder; wherein the electroless copper plating solution contains copper sulfate, hydrazine hydrate, complexing agent and ammonia water.
4. The method for preparing the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition according to claim 1, wherein the method comprises the following steps: the preparation method of the cobalt-coated hollow glass microsphere comprises the following specific steps:
(1) Placing the hollow glass beads in NaOH-Na 2CO3 mixed solution for degreasing treatment;
(2) Placing the deoiled hollow glass beads in NH 4 F-HCl mixed solution, and coarsening for 3-10 min to obtain coarsened hollow glass beads;
(3) The coarsened hollow glass beads are placed in stannous chloride-hydrochloric acid solution, and sensitized at the temperature of 25-60 ℃ for 5-10 min to obtain sensitized hollow glass beads;
(4) The sensitized hollow glass beads are placed in AgNO 3 -ammonia water, and activated for 5-20 min to obtain activated hollow glass beads;
(5) And placing the activated hollow glass beads in an electroless cobalt plating solution, performing electroless cobalt plating for 30-120 min at the temperature of 40-80 ℃ under stirring, washing with deionized water to neutrality, and performing vacuum drying to obtain the cobalt-coated hollow glass beads.
5. The titanium-based gradient lead dioxide composite electrode material for copper electrodeposition prepared by the method of any one of claims 1 to 4, which is characterized in that: the composite material comprises a titanium matrix, a Sn-Ru-Ta-ZrOx oxide bottom layer, a beta-PbO 2 -nano SnO 2 middle layer, an alpha-PbO 2 -copper coated graphite powder transition layer and a beta-PbO 2 -nano ZrN-cobalt coated hollow glass microsphere active layer from inside to outside.
6. The titanium-based gradient lead dioxide composite electrode material for copper electrodeposition according to claim 5, wherein: the mol ratio of the metal Sn, ru, ta and Zr in the underlying Sn-Ru-Ta-ZrOx oxide is (50-90): 1-10): 5-20): 4-20 respectively; the mass content of SnO 2 in the intermediate layer beta-PbO 2 -nano SnO 2 is 0.1-1.5 wt%; the mass content of the copper-clad graphite powder in the transition layer alpha-PbO 2 -copper-clad graphite powder is 1.0-3.2 wt%; the mass content of the nanometer ZrN particles in the active layer beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass bead is 0.6-1.8 wt%, and the content of the cobalt coated hollow glass bead is 0.5-5.0 wt%.
7. The titanium-based gradient lead dioxide composite electrode material for copper electrodeposition according to claim 5 or 6, wherein: the thickness of the Sn-Ru-Ta-ZrOx oxide bottom layer is 0.5-10 mu m, the thickness of the beta-PbO 2 -nano SnO 2 middle layer is 100-500 mu m, the thickness of the alpha-PbO 2 -copper coated graphite powder transition layer is 100-400 mu m, and the thickness of the beta-PbO 2 -nano ZrN-cobalt coated hollow glass bead active layer is 100-1200 mu m.
8. The titanium-based gradient lead dioxide composite electrode material for copper electrodeposition according to claim 5, wherein: the nano SnO 2 particles of the beta-PbO 2 -nano SnO 2 intermediate layer are spherical, and the particle size is 10-60 nm; the copper-coated graphite powder in the alpha-PbO 2 -copper-coated graphite powder transition layer is flaky, and the particle size is 1-20 mu m; the particle size of the nanometer ZrN particles in the beta-PbO 2 -nanometer ZrN-cobalt coated hollow glass bead active layer is 20-80 nm, the particles of the cobalt coated hollow glass bead are round or oval, and the particle size is 0.1-1.0 mm.
9. The titanium-based gradient lead dioxide composite electrode material for copper electrodeposition according to claim 5, wherein: the titanium substrate is made of TA1 or TA2, the appearance is net-shaped, the thickness is 0.5-4 mm, and silicon carbide sand or stainless steel shots are sprayed on the surface of the titanium substrate.
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| CN110453244A (en) * | 2019-09-04 | 2019-11-15 | 西安建筑科技大学 | A kind of composite interlayer that ti-lead dioxide anode can be made to lengthen the life and its preparation and application |
| CN111101153A (en) * | 2020-01-16 | 2020-05-05 | 昆明理工恒达科技股份有限公司 | Composite anode plate for copper electrodeposition and preparation method thereof |
| CN111893518A (en) * | 2020-09-14 | 2020-11-06 | 昆明理工恒达科技股份有限公司 | Fence type stainless steel base composite anode plate for copper electrodeposition and preparation method thereof |
| CN113293411A (en) * | 2021-05-24 | 2021-08-24 | 昆明理工大学 | Gradient composite lead dioxide anode plate and preparation method and application thereof |
| CN115287737A (en) * | 2022-08-03 | 2022-11-04 | 昆明理工大学 | Titanium-based gradient composite manganese dioxide anode plate and preparation method thereof |
| CN117107336A (en) * | 2023-09-01 | 2023-11-24 | 郑州大学 | Electroplating system for iron-cobalt-nickel alloy on surface of hollow glass bead |
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