CN108677221A - A kind of titanium-based β-MnO2Composite coating anode and preparation method thereof - Google Patents
A kind of titanium-based β-MnO2Composite coating anode and preparation method thereof Download PDFInfo
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- CN108677221A CN108677221A CN201810607761.1A CN201810607761A CN108677221A CN 108677221 A CN108677221 A CN 108677221A CN 201810607761 A CN201810607761 A CN 201810607761A CN 108677221 A CN108677221 A CN 108677221A
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- titanium
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- mno
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000010936 titanium Substances 0.000 title claims abstract description 101
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 101
- 238000000576 coating method Methods 0.000 title claims abstract description 92
- 239000011248 coating agent Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010410 layer Substances 0.000 claims abstract description 57
- 239000002131 composite material Substances 0.000 claims abstract description 54
- 239000011159 matrix material Substances 0.000 claims abstract description 40
- 229910018316 SbOx Inorganic materials 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000741 silica gel Substances 0.000 claims abstract description 8
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- 239000011229 interlayer Substances 0.000 claims abstract description 4
- 239000012141 concentrate Substances 0.000 claims description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 238000005245 sintering Methods 0.000 claims description 39
- 229910001868 water Inorganic materials 0.000 claims description 38
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 33
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 33
- 238000004821 distillation Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 229910006648 β-MnO2 Inorganic materials 0.000 claims description 32
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 30
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 30
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 29
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 25
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 25
- 239000011565 manganese chloride Substances 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 229940099607 manganese chloride Drugs 0.000 claims description 20
- 235000002867 manganese chloride Nutrition 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 14
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 12
- 235000021110 pickles Nutrition 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 238000005488 sandblasting Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 229910010062 TiCl3 Inorganic materials 0.000 claims 5
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims 5
- 230000001680 brushing effect Effects 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- 239000010970 precious metal Substances 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 32
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 30
- 235000019270 ammonium chloride Nutrition 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 238000005363 electrowinning Methods 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 3
- 235000014121 butter Nutrition 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002659 electrodeposit Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 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 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or physical properties
Abstract
A kind of titanium-based β MnO2Composite coating anode and preparation method thereof, the anode include the titanium copper-clad conducting beam (1) with conductive head (4), the titanium mesh plate (2) being welded in below copper conducting beam, the silica gel sheath (3) for being sleeved on titanium copper-clad conducting beam both ends；The titanium mesh plate (2) includes titanium net matrix, the gradient Ru Ti Sn SbOx middle layers coated on titanium net matrix surface and the β MnO coated on interlayer surfaces2Composite surface active layer.Anode prepared by the present invention is compared with traditional titanium-based noble metal coated anode, on the basis of not changing cell construction, electrolyte composition and working specification, electric conductivity significantly improves, tank voltage can reduce 0.1V, material cost reduces by 40%, current efficiency improves 1 3%, overcomes the excessively high disadvantage of precious metal oxide coating cost, energy large-scale application is in electrolytic industry.
Description
Technical field
The invention belongs to electrochemistry and technical field of wet metallurgy, and in particular to a kind of ammonium chloride solution system electroextraction
Metal titanium-based β-MnO2Composite coating anode plate and preparation method thereof.
Background technology
Ti-support metal oxide anode is also known as " dimensional stability anode " (DimentionallyStableAnode, abbreviation
DSA), it is usually to coat height in matrix surface by the methods of thermal decomposition, collosol and gel or electro-deposition using Titanium as matrix
The coated electrode of catalytically active metal oxides.20th century mid-term is started to the research of DSA, has been widely used in chlor-alkali work
The electrochemical industries such as industry, hydrometallurgy, plating, water process, electro synthesis and contaminant degradation.In sewage treatment field, electricity is urged
Changing oxidizing process has stronger oxidation and reducing power, and chemicals, which consumes, the valuable object such as lacks, and can also recycle metal
Matter.Therefore, it is applied in the wastewater treatment of the organic matters such as hydrocarbonaceous, aldehyde, phenol, ether, alcohol and dyestuff, especially in China's water pollution
Under the serious and severe situation of water resources shortage, Electrocatalytic Oxidation treated sewage will bring huge economic benefit and society
Benefit.DSA occupies the overwhelming majority in anode used by electrocatalytic oxidation treated sewage at present.In addition to sewage disposal, useless
If battery recycling field, the process problem in face of largely scrapping lead-acid accumulator will be made without scientific and reasonable disposition
At serious environmental disruption and the wasting of resources.Therefore, how clean and effective recycling lead-acid accumulator becomes current research hot spot,
For from the angle of environmental protection and the utilization of resources, the recycling of waste lead acid battery all has great importance.Correlative study
Show directly be reduced into metallic lead as the scrap lead cream in the electrode system of anode, being positioned on cathode plate in DSA, it should
Method simplifies the flow of scrap lead cream recycling, is entirely capable of avoiding the lead dust generated in pyrogenic process removal process and two in whole process
The consumption of the discharge of the pollutants such as sulfur oxide, chemical reagent is few, and electrolyte can reuse after filtering, is suitble to rule
Modelling produces.
The research of DSA is concentrated mainly in the research of the precious metal oxide coatings such as ruthenium, iridium at present, wherein electrolytic industry
It is IrO to analyse the best coating of oxygen anodes2-Ta2O5Composite oxide coating has higher analysis oxygen electro-catalysis in aqueous solution
Activity and electrochemical stability, can under acid stronger solution, high current density steady operation.But there is life in such electrode
The excessively high disadvantage that do not grown with service life of production cost, especially service life is shorter in the electrolysis of ammonium chloride solution system, and not
It can inhibit the generation of chlorine.In order to meet the needs of electrolytic industry is to DSA, there is an urgent need for reducing the production cost of DSA, therefore people is studied
Member studies base metal oxide coating, wherein with the most study of tin system and lead series oxide coating.But such
Coating limits its large-scale promotion application the problem of existing tank voltage is excessively high in actual use, short life.To sum up
Described, often there is clear advantage and defect in component and the single DSA of structure, limit its extensive use industrially.
Invention content
For above-mentioned existing DSA there are the shortcomings that, the present invention is intended to provide a kind of catalytic activity is excellent, service life is long,
The low ammonium chloride solution system electroextraction metal titanium-based β-MnO of tank voltage in electrolytic process2Composite coating anode plate and its
Preparation method.
The technical solution adopted by the present invention is as follows：
A kind of titanium-based β-MnO2Composite coating anode includes the titanium copper-clad conducting beam with conductive head, is welded in copper conducting beam
Following titanium mesh plate, the silica gel sheath for being sleeved on titanium copper-clad conducting beam both ends；The titanium mesh plate includes titanium net matrix, is coated on titanium net
The gradient Ru-Ti-Sn-SbOx middle layers of matrix surface and the β-MnO coated on interlayer surfaces2Composite surface active layer.
The thickness of gradient Ru-Ti-Sn-SbOx middle layers of the present invention is 20~40 μm, β-MnO2Composite surface activity
Layer thickness be 50~
200μm.The thickness of the titanium net matrix is 1-6mm, and mesh nominal dimension is 5-10mm.
Titanium-based β-MnO of the present invention2The preparation method of composite coating anode, method and step are as follows：
A. oil removing, descale, acid-wash activation processing are carried out to titanium net matrix：By titanium net matrix be put into mass concentration 10~
30~90min of oil removing in 30% NaOH solution is then placed in 1~3min of immersion in pickle and removes oxide film dissolving, is finally putting into
It is dense that 2h~3h is boiled in the HCl solution of mass concentration 10~30%, rinsed repeatedly with deionized water after taking-up and is soaked in quality
It is spare in the oxalic acid solution of degree 2%；The component and volume ratio of the pickle be：H2O:HNO3:HF=(4~6):(3~5):
1)；
B. thermal decomposition method is used to prepare gradient Ru-Ti-Sn-SbOx middle layers：By TiCl3、RuCl3·H2O、SnCl4·
5H2O and SbCl3It is added in concentrated hydrochloric acid in five kinds of different ratios to being completely dissolved, isopropanol solvent is then added, using rotation
Evaporimeter removes the moisture of solution, obtains five kinds of presoma concentrates, five kinds of presoma concentrates are successively painted on through step a
The titanium net matrix surface of processing is simultaneously successively sintered, and obtains gradient Ru-Ti-Sn-SbOx middle layers；Prepare the concentration of the first presoma
The substance of liquid is n (TiCl in molar ratio3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=56:24:18:2, system
The material mol ratio of standby second of presoma concentrate is n (TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n
(SbCl3)=42:18:36:4；The material mol ratio for preparing the third presoma concentrate is n (TiCl3)：n(RuCl3·
H2O)：n(SnCl4·5H2O)：n(SbCl3)=35:15:45:5, the material mol ratio for preparing the 4th kind of presoma concentrate is n
(TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=28:12:54:6, prepare the 5th kind of presoma concentration
The material mol ratio of liquid is n (TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=14:6:72:8；By
A kind of presoma concentrate is painted on titanium net matrix surface and obtains first coating, dries and first sintering, then by second
Presoma concentrate is painted in first coating, obtains second coating, dries and second is sintered, later by the third presoma
Concentrate is painted in second coating, obtains third coating, dries and third time is sintered；The 4th kind of presoma concentrate is applied again
It brushes on third coating, obtaining the 4th coating, dries and the 4th sintering, the 5th kind of presoma concentrate is finally painted on the
On four coatings, the 5th coating is obtained, dry and the 5th sintering is to get to gradient Ru-Ti-Sn-SbOx middle layers；
C. thermal decomposition method is used to prepare β-MnO2Composite surface active layer：By MnCl2·4H2O is added in concentrated hydrochloric acid to complete
Then nanometer MoO is added in dissolving3Or nanometer WO3And isopropanol solvent, the moisture of solution is removed using Rotary Evaporators, obtains chlorine
Change manganese presoma concentrate, which is painted on the titanium net gradient Ru-Ti-Sn- through step b processing
In SbOx middle layers, dry 1~5min in 100~120 DEG C of baking ovens, place into sintering 5 in 200~300 DEG C of Muffle furnace~
10min；Above-mentioned coating and sintering process 20~30 times are repeated, last time sintering is sintered 1~2h at 350 DEG C, obtains β-MnO2
Composite surface active layer；
D. weld together by titanium copper-clad conducting beam (1) and through step c processing titanium mesh plate obtained, and titanium copper-clad is conductive
It is wrapped up to get to titanium-based β-MnO with silica gel sheath (3) at beam (1) both ends2Composite coating anode.
The method of the present invention is carrying out surface sand-blasting process using preceding to the titanium net matrix with sand-blasting machine.Step b and step c
The temperature of the described Rotary Evaporators distillation is 80~110 DEG C, and rotary distillation bottle rotating speed is 100~300 turns/time, distillation it is true
Reciprocal of duty cycle is 0.098Mpa, 0.5~2.5h of distillation time.Drying described in step b be dry 1 in 100~120 DEG C of baking ovens~
5min, the sintering are 5~10min of sintering in 500 DEG C of Muffle furnace.Manganese chloride presoma concentrate described in step c is pressed
It is 20-50mg/cm according to manganese chloride coated weight2To prepare.Nano-sized molybdenum oxide or nano tungsten trioxide described in step c are sheet
Particle, grain size is in 180nm~400nm, and nano-sized molybdenum oxide particle or nano tungsten trioxide particle are in β-MnO2Composite surface is lived
The mass content of property layer accounts for 0.5~2.5wt.%.
The present invention has the following advantages that compared with prior art：
1, it prepares presoma concentrate using Rotary Evaporators and is coated on titanium net matrix surface, the distribution of thermal decomposition oxide is more
Uniformly and it can effectively avoid the problem of Titanium base is quickly aoxidized because of water vapour.
2, gradient Ru-Ti-Sn-SbOx middle layers are introduced by lamellar composite mode, Titanium base is effectively prevented to use
It generates oxygen in the process and generates TiO2DSA passivation failures caused by film, extend the service life of electrode, and improve
The current lead-through efficiency of entire electrode and the infiltration for inhibiting chlorion.
3, nano-sized molybdenum oxide particle and nano tungsten trioxide introduce β-MnO2The internal stress in coating is reduced in coating,
The generation of coating crackle is avoided, and greatly improves the electric conductivity and corrosion resistance of composite deposite, extends anode
Service life.
4, the novel DSA anodic coatings catalytic performance that prepared by the method for the present invention is excellent, and service life is long, electrolytic process bracket groove
Voltage is low, can inhibit the generation of chlorine, is conducive to the generation of nitrogen, environmental-friendly, overcomes precious metal oxide coating cost
Excessively high disadvantage.
Ammonium chloride solution system electroextraction metal titanium-based β-MnO prepared by the present invention2Composite coating anode and tradition
Titanium-based noble metal coated anode compare, it is conductive not changing cell construction, electrolyte composition and on the basis of working specification
Property significantly improve, tank voltage can reduce 0.1V, and material cost reduces by 40%, and current efficiency improves 1-3%, can large-scale application in
In electrolytic industry.
Description of the drawings
Fig. 1 is the novel DSA schematic diagrames of the present invention.
Specific implementation mode
As shown in Figure 1, the titanium-based β-MnO of the present invention2Composite coating anode plate includes that the titanium copper-clad with conductive head 4 is conductive
Beam 1, the titanium mesh plate 2 being welded in below copper conducting beam, the silica gel sheath 3 for being sleeved on titanium copper-clad conducting beam both ends.The titanium mesh plate 2 wraps
Include titanium net matrix, the gradient Ru-Ti-Sn-SbOx middle layers coated on titanium net matrix surface and coated on the β-of interlayer surfaces
MnO2Composite surface active layer.The thickness of the gradient Ru-Ti-Sn-SbOx middle layers is 20~40 μm, β-MnO2Composite surface
Active layer thickness is 50~200 μm.The thickness of the titanium net matrix is 1-6mm, and the mesh of titanium net matrix can be diamond-shaped meshes
Or cylinder hole, mesh nominal dimension are that (diamond-shaped meshes nominal dimension refers to its maximum diagonal length, round mesh to 5-10mm
Nominal dimension refers to its diameter).
Embodiment 1
A kind of ammonium chloride solution system electroextraction metal titanium-based β-MnO2The preparation method of composite coating anode, step
It is as follows：
A. Titanium base pre-treatment：By 2mm, thick, diamond-shaped meshes aperture 6mm titanium net matrix first carries out surface spray with sand-blasting machine
Sand processing, improves its surface roughness, carries out oil removing, descale, acid-wash activation processing to titanium net matrix later, specially first
Titanium net matrix is put into oil removing 60min in the NaOH solution of mass concentration 20%, is then placed in pickle and impregnates 3min removals
Oxidation film is finally putting into the HCl solution of mass concentration 30% and boils 2h, is rinsed and is soaked in repeatedly with deionized water after taking-up
It is spare in the oxalic acid solution of mass concentration 2%；The component and volume ratio of the pickle be：H2O:HNO3:HF=4:5:1.
B. thermal decomposition method is used to prepare gradient Ru-Ti-Sn-SbOx middle layers：By titanium trichloride (TiCl3), ruthenium trichloride
(RuCl3·H2O), butter of tin (SnCl4·5H2) and antimony trichloride (SbCl O3) be added in concentrated hydrochloric acid in five kinds of different ratios
To being completely dissolved, isopropanol solvent is then added, the moisture of solution is removed using Rotary Evaporators, obtains five kinds of presoma concentrations
Five kinds of presoma concentrates are successively painted on the titanium net matrix surface through step a processing and are successively sintered, obtain gradient by liquid
Ru-Ti-Sn-SbOx middle layers.The temperature of Rotary Evaporators distillation is 100 DEG C, and rotary distillation bottle rotating speed is 200 turns/time, distillation
Vacuum degree be 0.098Mpa, distillation time 2.5h.The substance for preparing the first presoma concentrate is n in molar ratio
(TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=56:24:18:2, prepare second of presoma concentration
The material mol ratio of liquid is n (TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=42:18:36:4；It prepares
The material mol ratio of the third presoma concentrate is n (TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)
=35:15:45:5, the material mol ratio for preparing the 4th kind of presoma concentrate is n (TiCl3)：n(RuCl3·H2O)：n
(SnCl4·5H2O)：n(SbCl3)=28:12:54:6, the material mol ratio for preparing the 5th kind of presoma concentrate is n
(TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=14:6:72:8；The first presoma concentrate is applied
It brushes and obtains first coating in titanium net matrix surface, dry simultaneously first sintering, be then painted on second of presoma concentrate
In first coating, second coating is obtained, dries and second is sintered, the third presoma concentrate is painted on the second painting later
On layer, third coating is obtained, dries and third time is sintered；The 4th kind of presoma concentrate is painted on third coating again, is obtained
To the 4th coating, dries and the 4th time is sintered, finally the 5th kind of presoma concentrate is painted on the 4th coating, obtains the 5th
Coating, is dried and the 5th sintering is to get the gradient Ru-Ti-Sn-SbOx middle layers for being 30 μm to thickness.The drying of coating is
The dry 1min in 120 DEG C of baking ovens, sintering is to be sintered 7min in 500 DEG C of Muffle furnace.
C. thermal decomposition method is used to prepare β-MnO2Composite surface active layer：By manganese chloride (MnCl2·4H2O concentrated hydrochloric acid) is added
In to being completely dissolved, nano-sized molybdenum oxide (MoO is then added3) or nano tungsten trioxide (WO3) and isopropanol solvent, using rotation
Turn evaporimeter remove solution moisture, obtain manganese chloride presoma concentrate, by the manganese chloride presoma concentrate be painted on through
In the titanium net gradient Ru-Ti-Sn-SbOx middle layers of step b processing, make painting thickness and uniform, it is dry in 120 DEG C of baking ovens
2min is placed into 250 DEG C of Muffle furnace and is sintered 8min；Above-mentioned coating and sintering process 25 times are repeated, i.e., often coats one layer of chlorine
Change manganese presoma concentrate just be sintered once, each drying coat all controls oven temperature at 100~120 DEG C, drying time 1
~5min, intermediate sintering every time all control 200~300 DEG C, 5~10min of sintering time of muffle furnace, and last time sintering exists
350 DEG C of sintering 2h, obtain the β-MnO that thickness is 150 μm2Composite surface active layer.The temperature of Rotary Evaporators distillation is 100
DEG C, rotary distillation bottle rotating speed is 200 turns/time, and the vacuum degree of distillation is 0.098Mpa, distillation time 2.5h.Manganese chloride presoma
Concentrate is 40mg/cm according to manganese chloride coated weight2To prepare.Nano-sized molybdenum oxide or nano tungsten trioxide are sheet-like particle,
Grain size is in 200nm~300nm, and nano-sized molybdenum oxide particle or nano tungsten trioxide particle are in β-MnO2Composite surface active layer
Mass content accounts for 2.0wt.%.
D. weld together by titanium copper-clad conducting beam 1 and through step c processing titanium mesh plate obtained, and by titanium copper-clad conducting beam
It is wrapped up to get to titanium-based β-MnO with silica gel sheath 3 at 1 both ends2Composite coating anode plate.
Ammonium chloride solution system electroextraction metal manufactured in the present embodiment titanium-based β-MnO2Composite coating anode is in manganese
In electrolyte, electrolytic condition is that catholyte manganese ion concentration is 40g/L, ammonium chloride concentration 60g/L, electrolysis temperature 30
DEG C, pH 6.50, anolyte manganese ion concentration is 20g/L, ammonium chloride concentration 120g/L, hydrochloric acid 30g/L, electrolysis temperature
Degree is 30 DEG C, using anion membrane electrolytic bath electrodeposit metals manganese, titanium-based β-MnO2The electricity effect of composite coating anode is than tradition
Titanium-based iridium tantalum ru oxide precious metal anode plate improves 1%, significantly inhibits the generation of chlorine, the low 100mV of tank voltage, service life
Extend 1 times.
Embodiment 2
A kind of ammonium chloride solution system electroextraction metal titanium-based β-MnO2The preparation method of composite coating anode, step
It is as follows：
A. Titanium base pre-treatment：By 6mm, thick, diamond-shaped meshes aperture 10mm titanium net matrix first carries out surface spray with sand-blasting machine
Sand processing, improves its surface roughness, carries out oil removing, descale, acid-wash activation processing to titanium net matrix later, specially first
Titanium net matrix is put into oil removing 30min in the NaOH solution of mass concentration 30%, is then placed in pickle and impregnates 2min removals
Oxidation film is finally putting into the HCl solution of mass concentration 20% and boils 2.5h, is rinsed and is impregnated repeatedly with deionized water after taking-up
It is spare in the oxalic acid solution of mass concentration 2%；The component and volume ratio of the pickle be：H2O:HNO3:HF=6:3:1.
B. thermal decomposition method is used to prepare gradient Ru-Ti-Sn-SbOx middle layers：By titanium trichloride (TiCl3), ruthenium trichloride
(RuCl3·H2O), butter of tin (SnCl4·5H2) and antimony trichloride (SbCl O3) be added in concentrated hydrochloric acid in five kinds of different ratios
To being completely dissolved, isopropanol solvent is then added, the moisture of solution is removed using Rotary Evaporators, obtains five kinds of presoma concentrations
Five kinds of presoma concentrates are successively painted on the titanium net matrix surface through step a processing and are successively sintered, obtain gradient by liquid
Ru-Ti-Sn-SbOx middle layers.The temperature of Rotary Evaporators distillation is 110 DEG C, and rotary distillation bottle rotating speed is 100 turns/time, distillation
Vacuum degree be 0.098Mpa, distillation time 0.5h.The substance for preparing the first presoma concentrate is n in molar ratio
(TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=56:24:18:2, prepare second of presoma concentration
The material mol ratio of liquid is n (TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=42:18:36:4；It prepares
The material mol ratio of the third presoma concentrate is n (TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)
=35:15:45:5, the material mol ratio for preparing the 4th kind of presoma concentrate is n (TiCl3)：n(RuCl3·H2O)：n
(SnCl4·5H2O)：n(SbCl3)=28:12:54:6, the material mol ratio for preparing the 5th kind of presoma concentrate is n
(TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=14:6:72:8；The first presoma concentrate is applied
It brushes and obtains first coating in titanium net matrix surface, dry simultaneously first sintering, be then painted on second of presoma concentrate
In first coating, second coating is obtained, dries and second is sintered, the third presoma concentrate is painted on the second painting later
On layer, third coating is obtained, dries and third time is sintered；The 4th kind of presoma concentrate is painted on third coating again, is obtained
To the 4th coating, dries and the 4th time is sintered, finally the 5th kind of presoma concentrate is painted on the 4th coating, obtains the 5th
Coating, is dried and the 5th sintering is to get the gradient Ru-Ti-Sn-SbOx middle layers for being 20 μm to thickness.The drying of coating is
The dry 5min in 100 DEG C of baking ovens, sintering is to be sintered 5min in 500 DEG C of Muffle furnace.
C. thermal decomposition method is used to prepare β-MnO2Composite surface active layer：By manganese chloride (MnCl2·4H2O concentrated hydrochloric acid) is added
In to being completely dissolved, nano-sized molybdenum oxide (MoO is then added3) or nano tungsten trioxide (WO3) and isopropanol solvent, using rotation
Turn evaporimeter remove solution moisture, obtain manganese chloride presoma concentrate, by the manganese chloride presoma concentrate be painted on through
In the titanium net gradient Ru-Ti-Sn-SbOx middle layers of step b processing, make painting thickness and uniform, it is dry in 100 DEG C of baking ovens
5min is placed into 200 DEG C of Muffle furnace and is sintered 10min；Above-mentioned coating and sintering process 20 times are repeated, i.e., often coats one layer of chlorine
Change manganese presoma concentrate just be sintered once, each drying coat all controls oven temperature at 100~120 DEG C, drying time 1
~5min, intermediate sintering every time all control 200~300 DEG C, 5~10min of sintering time of muffle furnace, and last time sintering exists
350 DEG C of sintering 1.5h, obtain the β-MnO that thickness is 50 μm2Composite surface active layer.The temperature of Rotary Evaporators distillation is 110
DEG C, rotary distillation bottle rotating speed is 100 turns/time, and the vacuum degree of distillation is 0.098Mpa, distillation time 0.5h.Manganese chloride presoma
Concentrate is 20mg/cm according to manganese chloride coated weight2To prepare.Nano-sized molybdenum oxide or nano tungsten trioxide are sheet-like particle,
Grain size is in 300nm~400nm, and nano-sized molybdenum oxide particle or nano tungsten trioxide particle are in β-MnO2Composite surface active layer
Mass content accounts for 0.5wt.%.
D. weld together by titanium copper-clad conducting beam 1 and through step c processing titanium mesh plate obtained, and by titanium copper-clad conducting beam
It is wrapped up to get to titanium-based β-MnO with silica gel sheath 3 at 1 both ends2Composite coating anode plate.
Ammonium chloride solution system electroextraction metal manufactured in the present embodiment titanium-based β-MnO2Composite coating anode is in manganese
In electrolyte, electrolytic condition is that catholyte manganese ion concentration is 40g/L, ammonium chloride concentration 60g/L, electrolysis temperature 30
DEG C, pH 6.50, anolyte manganese ion concentration is 20g/L, ammonium chloride concentration 120g/L, hydrochloric acid 30g/L, electrolysis temperature
Degree is 30 DEG C, using anion membrane electrolytic bath electrodeposit metals manganese, titanium-based β-MnO2The electricity effect of composite coating anode is than tradition
Titanium-based iridium tantalum ru oxide precious metal anode plate improves 1.5%, significantly inhibits the generation of chlorine, the low 50mV of tank voltage, longevity
Life extends 2 times.
Embodiment 3
A kind of ammonium chloride solution system electroextraction metal titanium-based β-MnO2The preparation method of composite coating anode, step
It is as follows：
A. Titanium base pre-treatment：By 1mm, the titanium net matrix of thick, round mesh aperture 5mm first carries out surface spray with sand-blasting machine
Sand processing, improves its surface roughness, carries out oil removing, descale, acid-wash activation processing to titanium net matrix later, specially first
Titanium net matrix is put into oil removing 90min in the NaOH solution of mass concentration 10%, is then placed in pickle and impregnates 1min removals
Oxidation film is finally putting into the HCl solution of mass concentration 10% and boils 3h, is rinsed and is soaked in repeatedly with deionized water after taking-up
It is spare in the oxalic acid solution of mass concentration 2%；The component and volume ratio of the pickle be：H2O:HNO3:HF=5:4:1.
B. thermal decomposition method is used to prepare gradient Ru-Ti-Sn-SbOx middle layers：By titanium trichloride (TiCl3), ruthenium trichloride
(RuCl3·H2O), butter of tin (SnCl4·5H2) and antimony trichloride (SbCl O3) be added in concentrated hydrochloric acid in five kinds of different ratios
To being completely dissolved, isopropanol solvent is then added, the moisture of solution is removed using Rotary Evaporators, obtains five kinds of presoma concentrations
Five kinds of presoma concentrates are successively painted on the titanium net matrix surface through step a processing and are successively sintered, obtain gradient by liquid
Ru-Ti-Sn-SbOx middle layers.The temperature of Rotary Evaporators distillation is 80 DEG C, and rotary distillation bottle rotating speed is 300 turns/time, distillation
Vacuum degree be 0.098Mpa, distillation time 2h.The substance for preparing the first presoma concentrate is n (TiCl in molar ratio3)：
n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=56:24:18:2, prepare the substance of second of presoma concentrate
Molar ratio is n (TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=42:18:36:4；Before preparing the third
The material mol ratio for driving body concentrate is n (TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=35:15:
45:5, the material mol ratio for preparing the 4th kind of presoma concentrate is n (TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：
n(SbCl3)=28:12:54:6, the material mol ratio for preparing the 5th kind of presoma concentrate is n (TiCl3)：n(RuCl3·
H2O)：n(SnCl4·5H2O)：n(SbCl3)=14:6:72:8；The first presoma concentrate is painted on titanium net matrix surface
It obtains first coating, dries and first sintering, then second of presoma concentrate is painted in first coating, obtain the
Two coatings, are dried and second is sintered, the third presoma concentrate is painted in second coating later, obtain third painting
Layer, is dried and third time is sintered；The 4th kind of presoma concentrate is painted on third coating again, obtains the 4th coating, is dried
And the 4th sintering, finally the 5th kind of presoma concentrate is painted on the 4th coating, obtains the 5th coating, drying and the 5th
Secondary sintering is to get the gradient Ru-Ti-Sn-SbOx middle layers for being 40 μm to thickness.The drying of coating is done in 110 DEG C of baking ovens
Dry 3min, sintering are to be sintered 10min in 500 DEG C of Muffle furnace.
C. thermal decomposition method is used to prepare β-MnO2Composite surface active layer：By manganese chloride (MnCl2·4H2O concentrated hydrochloric acid) is added
In to being completely dissolved, nano-sized molybdenum oxide (MoO is then added3) or nano tungsten trioxide (WO3) and isopropanol solvent, using rotation
Turn evaporimeter remove solution moisture, obtain manganese chloride presoma concentrate, by the manganese chloride presoma concentrate be painted on through
In the titanium net gradient Ru-Ti-Sn-SbOx middle layers of step b processing, make painting thickness and uniform, it is dry in 110 DEG C of baking ovens
1min is placed into 300 DEG C of Muffle furnace and is sintered 5min；Above-mentioned coating and sintering process 30 times are repeated, i.e., often coats one layer of chlorine
Change manganese presoma concentrate just be sintered once, each drying coat all controls oven temperature at 100~120 DEG C, drying time 1
~5min, intermediate sintering every time all control 200~300 DEG C, 5~10min of sintering time of muffle furnace, and last time sintering exists
350 DEG C of sintering 1h, obtain the β-MnO that thickness is 200 μm2Composite surface active layer.The temperature of Rotary Evaporators distillation is 80 DEG C,
Rotary distillation bottle rotating speed is 300 turns/time, and the vacuum degree of distillation is 0.098Mpa, distillation time 2h.Manganese chloride presoma concentrate
It is 50mg/cm according to manganese chloride coated weight2To prepare.Nano-sized molybdenum oxide or nano tungsten trioxide are sheet-like particle, and grain size exists
180nm~250nm, nano-sized molybdenum oxide particle or nano tungsten trioxide particle are in β-MnO2The quality of composite surface active layer contains
Amount accounts for 2.5wt.%.
Ammonium chloride solution system electroextraction metal manufactured in the present embodiment titanium-based β-MnO2Composite coating anode is solid
In phase electrolytic recovery waste lead acid battery lead cream, electrolytic condition is that cathode is the stainless steel cathode cylinder equipped with lead plaster, and ammonium chloride is dense
Degree is 80g/L, ethylenediamine 20g/L, ammonium acetate 180g/L, and electrolysis temperature is 40 DEG C, pH 6.50, anode electricity current density
For 600A/m2, titanium-based β-MnO2The electricity effect of composite coating anode is improved than traditional titanium-based iridium tantalum ru oxide precious metal anode plate
2%, significantly inhibit the generation of chlorine, the purity of gained lead to be higher than 99.9%, the low 100mV of tank voltage, the service life extends 2 times.
Claims (9)
1. a kind of titanium-based β-MnO2Composite coating anode, which is characterized in that include the titanium copper-clad conducting beam (1) with conductive head (4),
The titanium mesh plate (2) that is welded in below copper conducting beam, the silica gel sheath (3) for being sleeved on titanium copper-clad conducting beam both ends；The titanium mesh plate (2)
Gradient Ru-Ti-Sn-SbOx middle layers including titanium net matrix, coated on titanium net matrix surface and coated on interlayer surfaces
β-MnO2Composite surface active layer.
2. a kind of titanium-based β-MnO according to claim 12Composite coating anode, which is characterized in that the gradient Ru-Ti-
The thickness of Sn-SbOx middle layers is 20~40 μm, β-MnO2Composite surface active layer thickness is 50~200 μm.
3. a kind of titanium-based β-MnO according to claim 12Composite coating anode, which is characterized in that the titanium net matrix
Thickness is 1-6mm, and mesh nominal dimension is 5-10mm.
4. such as a kind of titanium-based β-MnO of claims 1 to 3 any one of them2The preparation method of composite coating anode, feature exist
In method and step is as follows：
A. oil removing, descale, acid-wash activation processing are carried out to titanium net matrix：Titanium net matrix is put into mass concentration 10~30%
NaOH solution in 30~90min of oil removing, be then placed in pickle impregnate 1~3min remove oxide film dissolving, be finally putting into quality
2h~3h is boiled in the HCl solution of concentration 10~30%, is rinsed repeatedly with deionized water after taking-up and is soaked in mass concentration 2%
Oxalic acid solution in it is spare；The component and volume ratio of the pickle be：H2O:HNO3:HF=(4~6):(3~5):1)；
B. thermal decomposition method is used to prepare gradient Ru-Ti-Sn-SbOx middle layers：By TiCl3、RuCl3·H2O、SnCl4·5H2O and
SbCl3It is added in concentrated hydrochloric acid in five kinds of different ratios to being completely dissolved, isopropanol solvent is then added, using Rotary Evaporators
The moisture for removing solution, obtains five kinds of presoma concentrates, and five kinds of presoma concentrates are successively painted on through step a processing
Titanium net matrix surface is simultaneously successively sintered, and obtains gradient Ru-Ti-Sn-SbOx middle layers；Prepare the object of the first presoma concentrate
Matter is n (TiCl in molar ratio3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=56:24:18:2, prepare second
The material mol ratio of kind presoma concentrate is n (TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=42:
18:36:4；The material mol ratio for preparing the third presoma concentrate is n (TiCl3)：n(RuCl3·H2O)：n(SnCl4·
5H2O)：n(SbCl3)=35:15:45:5, the material mol ratio for preparing the 4th kind of presoma concentrate is n (TiCl3)：n
(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=28:12:54:6, the substance for preparing the 5th kind of presoma concentrate rubs
You are than being n (TiCl3)：n(RuCl3·H2O)：n(SnCl4·5H2O)：n(SbCl3)=14:6:72:8；By the first presoma
Concentrate is painted on titanium net matrix surface and obtains first coating, dries simultaneously first sintering, then concentrates second of presoma
Liquid is painted in first coating, obtains second coating, dries and second is sintered, later by the third presoma concentrate brushing
In in second coating, obtaining third coating, dries and third time is sintered；The 4th kind of presoma concentrate third is painted on again to apply
On layer, the 4th coating is obtained, dries and the 4th time is sintered, finally the 5th kind of presoma concentrate is painted on the 4th coating,
It obtains the 5th coating, dries and the 5th sintering is to get to gradient Ru-Ti-Sn-SbOx middle layers；
C. thermal decomposition method is used to prepare β-MnO2Composite surface active layer：By MnCl2·4H2O is added in concentrated hydrochloric acid to completely molten
Then nanometer MoO is added in solution3Or nanometer WO3And isopropanol solvent, the moisture of solution is removed using Rotary Evaporators, obtains chlorination
The manganese chloride presoma concentrate is painted on the titanium net gradient Ru-Ti-Sn-SbOx through step b processing by manganese presoma concentrate
In middle layer, dry 1~5min in 100~120 DEG C of baking ovens, place into sintering 5 in 200~300 DEG C of Muffle furnace~
10min；Above-mentioned coating and sintering process 20~30 times are repeated, last time sintering is sintered 1~2h at 350 DEG C, obtains β-MnO2
Composite surface active layer；
D. weld together by titanium copper-clad conducting beam (1) and through step c processing titanium mesh plate obtained, and by titanium copper-clad conducting beam
(1) both ends are wrapped up with silica gel sheath (3) to get to titanium-based β-MnO2Composite coating anode.
5. a kind of preparation method of titanium-based β-MnO2 composite coating anodes according to claim 4, which is characterized in that described
Titanium net matrix is carrying out surface sand-blasting process using preceding with sand-blasting machine.
6. a kind of preparation method of titanium-based β-MnO2 composite coating anodes according to claim 4, feature exist
The temperature of Rotary Evaporators distillation described in, step b and step c is 80~110 DEG C, and rotary distillation bottle rotating speed is 100~300
Turn/time, the vacuum degree of distillation is 0.098Mpa, 0.5~2.5h of distillation time.
7. a kind of titanium-based β-MnO according to claim 42The preparation method of composite coating anode, feature exist
In the drying described in step b is dry 1~5min in 100~120 DEG C of baking ovens, and the sintering is in 500 DEG C of Muffle furnace
It is sintered 5~10min.
8. a kind of titanium-based β-MnO according to claim 42The preparation method of composite coating anode, feature exist
In manganese chloride presoma concentrate described in step c is 20-50mg/cm according to manganese chloride coated weight2To prepare.
9. a kind of titanium-based β-MnO according to claim 42The preparation method of composite coating anode, feature exist
In nano-sized molybdenum oxide or nano tungsten trioxide described in step c are sheet-like particle, and grain size is in 180nm~400nm, nanometer three
Molybdenum oxide particle or nano tungsten trioxide particle are in β-MnO2The mass content of composite surface active layer accounts for 0.5~2.5wt.%.
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