CN114457368B - Coated titanium anode for zinc electrodeposition and preparation method thereof - Google Patents
Coated titanium anode for zinc electrodeposition and preparation method thereof Download PDFInfo
- Publication number
- CN114457368B CN114457368B CN202210218316.2A CN202210218316A CN114457368B CN 114457368 B CN114457368 B CN 114457368B CN 202210218316 A CN202210218316 A CN 202210218316A CN 114457368 B CN114457368 B CN 114457368B
- Authority
- CN
- China
- Prior art keywords
- iro
- ruo
- titanium
- titanium substrate
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010936 titanium Substances 0.000 title claims abstract description 195
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 193
- 239000011701 zinc Substances 0.000 title claims abstract description 41
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004070 electrodeposition Methods 0.000 title claims description 27
- 239000000758 substrate Substances 0.000 claims abstract description 111
- 238000000576 coating method Methods 0.000 claims abstract description 74
- 239000011248 coating agent Substances 0.000 claims abstract description 73
- 230000007704 transition Effects 0.000 claims abstract description 48
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 161
- 239000000243 solution Substances 0.000 claims description 94
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 35
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 34
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 20
- 238000007747 plating Methods 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 20
- 239000004332 silver Substances 0.000 claims description 20
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000005498 polishing Methods 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 10
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 10
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 10
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 10
- 239000011229 interlayer Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 3
- 238000005363 electrowinning Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 5
- 230000035772 mutation Effects 0.000 abstract description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 47
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 24
- 239000011572 manganese Substances 0.000 description 18
- 238000009835 boiling Methods 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 9
- 235000006408 oxalic acid Nutrition 0.000 description 8
- 238000005554 pickling Methods 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000008399 tap water Substances 0.000 description 8
- 235000020679 tap water Nutrition 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 6
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
- C25B11/063—Valve metal, e.g. titanium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
Abstract
The invention discloses a coated titanium anode for zinc electrowinning and a preparation method thereof, wherein the coated titanium anode is sequentially provided with an intermediate layer Ti-Ag and a transition layer IrO 2 ‑RuO 2 -Ag and a surface active layer; the surface active layer is made of IrO 2 、RuO 2 、SnO 2 、MnO 2 The surface active layer is divided into two layers, and the two layers are respectively [ IrO from inside to outside ] 2 ‑RuO 2 ‑SnO 2 ]，[IrO 2 ‑RuO 2 ‑MnO 2 ]. Preparing Ti-Ag intermediate layer and IrO on the surface of the treated titanium substrate in turn by adopting a chemical reduction method 2 ‑RuO 2 Ag transition layer and IrO 2 ‑RuO 2 ‑SnO 2 ]、[IrO 2 ‑RuO 2 ‑MnO 2 ]A surface active layer. RuO in oxide coating 2 ‑IrO 2 The content is gradually increased from inside to outside, the effective utilization rate of the active components is improved, the cost is reduced, the gradient structure can effectively slow down the stress mutation on the joint surface of the coating and the matrix, and the stability of the coating structure is improved.
Description
Technical Field
The invention belongs to the technical field of chemistry, and particularly relates to a coated titanium anode for zinc electrodeposition and a preparation method thereof.
Background
Titanium anodes, also known as Dimensionally Stable Anodes (DSAs), consist of a metal substrate and an oxide coating attached to the surface thereof. The matrix is generally made of metallic titanium, and the oxide coating is generally composed of an active component and an inert component for stabilizing. The texture of the oxide coating is a key factor in determining the performance of the anode, including electrochemical activity and corrosion resistance, both of which are closely related to the composition and texture of the material. Ti/IrO 2 -Ta 2 O 5 The coating electrode is considered to be a very promising titanium anode for oxygen evolution, the substrate is pure titanium material, and the surface layer is composed of an active component IrO 2 And an inert component Ta for stabilization 2 O 5 The anode can replace lead anode, has wide application prospect in the fields of industrial electroplating, metal smelting, environmental protection, seawater electrolysis and the like, and is mainly used for the electrolysis process of high-corrosiveness acid solution, so that the anode is required to have extremely strong stability and good electrochemical catalytic activity.
The titanium polar plate is environment-friendly, stable in size, low in energy consumption and Ti/IrO (titanium/titanium oxide) 2 -RuCl 3 The titanium plate is a best electrode material for oxygen evolution in sulfuric acid solution at present, but the price of the titanium plate is higher than that of a lead-silver anode, and Ir and Ru have low reserves in the nature and are high in price. Compared with the traditional lead-silver anode plate, ti/IrO 2 - RuCl 3 The intensified electrolysis life of the anode plate is only increased by 20%, and the comprehensive accounting cost is still higher than that of the traditional lead-silver anode plate, so that the cost problem is still a barrier to the industrial application of the inert titanium anode plate. Find the substitutable base metal, reduce Ir and Ru consumption, optimize coating design and process control, improve the polar plate performance, lengthen the service life of the coating, finally realize reducing the use cost of the titanium polar plate, can realize the substitution of industrialization.
Disclosure of Invention
The first object of the present invention is to provide a coated titanium anode for zinc electrodeposition; the second aim is to provide a preparation method of the coated titanium anode for zinc electrodeposition.
The first object of the invention is achieved in that the coated titanium anode for zinc electrodeposition further comprises an intermediate layer, a transition layer and a surface active layer;
the intermediate layer is Ti-Ag;
the transition layer is IrO 2 -RuO 2 -Ag；
The surface active layer is formed by IrO 2 、RuO 2 、SnO 2 、MnO 2 The surface active layer is divided into two layers, and the two layers are respectively [ IrO from inside to outside ] 2 -RuO 2 -SnO 2 ]，[IrO 2 -RuO 2 -MnO 2 ]。
The second object of the present invention is achieved by comprising the steps of:
polishing, alkali washing and acid washing are carried out on a titanium substrate, and a Ti-Ag-containing intermediate layer titanium substrate is prepared by a chemical reduction method based on the treated titanium substrate;
step two, coating the coating liquid 1 on the titanium substrate containing the Ti-Ag intermediate layer obtained in the step one, and drying and roasting;
step three, repeating the step two for 3 times to obtain the intermediate layer containing Ti-Ag and IrO from inside to outside 2 -RuO 2 -a titanium substrate of an Ag transition layer;
step four, coating the coating liquid No. 2 on the titanium substrate in the step three, and drying and roasting;
step five, repeating the steps for 4 times to obtain the alloy containing Ti-Ag and IrO sequentially from inside to outside 2 -RuO 2 -Ag、[IrO 2 -RuO 2 -SnO 2 ]A coated titanium substrate;
step six, coating the coating liquid No. 3 on the titanium substrate obtained in the step five, and drying and roasting;
step seven, repeating the steps for six 5 times to obtain the alloy containing Ti-Ag and IrO from inside to outside 2 -RuO 2 -Ag、[IrO 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]A coated titanium anode;
the No. 1 coating liquid is as follows: 3-7g/L H 2 IrCl 6 、3-7g/L RuCl 3 、3-7g/L Ag(NO) 3 And V (n-butanol): v (absolute ethanol) =0.5-1.5:0.5-1.5;
the No. 2 coating liquid is as follows: 8-12g/L H 2 IrCl 6 、8-12g/L RuCl 3 、3-6g/L SnCl 4· 5H 2 O、3-6g/L Mn(NO 3 ) 2 And V (n-butanol): v (absolute ethanol) =0.5-1.5:0.5-1.5;
the No. 3 coating liquid is as follows: 12-16g/L H 2 IrCl 6 、12-16g/L RuCl 3 、8-12g/L Mn(NO 3 ) 2 And V (n-butanol): v (absolute ethanol) =0.5-1.5:0.5-1.5.
The specific operation is as follows:
step one, polishing, alkali washing and acid washing the titanium substrate, and preparing the Ti-Ag-containing intermediate layer titanium substrate by adopting a chemical reduction method based on the treated titanium substrate.
Step two, coating the coating liquid No. 1 on the titanium substrate containing the Ti-Ag intermediate layer obtained in the step one, drying for 10min at 120 ℃, and roasting for 20min at 450 ℃;
step three, repeating the step two for 3 times to obtain the intermediate layer containing Ti-Ag and IrO from inside to outside 2 -RuO 2 -a titanium substrate of an Ag transition layer;
step four, coating the coating liquid No. 2 on the titanium substrate in the step three, drying for 10min at 120 ℃, and roasting for 20min at 450 ℃;
step five, repeating the steps for 4 times to obtain the alloy containing Ti-Ag and IrO sequentially from inside to outside 2 -RuO 2 -Ag、[IrO 2 -RuO 2 -SnO 2 ]A coated titanium substrate;
step six, coating the coating liquid No. 3 on the titanium substrate obtained in the step five, drying for 10min at 120 ℃, and roasting for 20min at 450 ℃;
step seven, repeating the steps for six 5 times to obtain the alloy containing Ti-Ag and IrO from inside to outside 2 -RuO 2 -Ag、[IrO 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]A coated titanium anode;
the drying and roasting conditions are that the drying and roasting are carried out for 10min at 120 ℃ and then the roasting is carried out for 20min at 450 ℃.
Further, in the first step, the preparing the titanium substrate containing the Ti-Ag interlayer includes:
(1) Polishing the surface of the titanium substrate, and performing alkaline cleaning, degreasing and etching for later use; specifically, the titanium substrate was put into 5wt% Na 2 CO 3 Boiling in solution, alkali washing and degreasing for 0.5h, pickling in 10wt% boiling oxalic acid solution for 1.5h to remove surface oxide film, washing with tap water, deionized water and alcohol in sequence, and drying for later use;
(2) Dropping ammonia water with the concentration of 70-90mL/L into 15-25g/L silver nitrate solution, clarifying the solution to obtain silver ammonia solution, and adding the silver ammonia solution into an equal volume of potassium sodium tartrate solution with the concentration of 90-110g/L to obtain silver plating solution;
(3) Placing the pretreated titanium plate into silver plating solution, standing for 1-1.5h at 20-35 ℃ to load a layer of uniform and compact simple substance Ag on the surface of the titanium plate, and obtaining a titanium substrate containing a Ti-Ag intermediate layer;
further, in the second step, the composition contains chloroiridic acid (H 2 IrCl 6 ) Ruthenium trichloride (RuCl) 3 ) Silver nitrate (Ag (NO) 3 ) The No. 1 coating liquid prepared by mixing n-butanol and absolute ethyl alcohol comprises the following components: 3-7g/L H 2 IrCl 6 、3-7g/L RuCl 3 、3-7g/L Ag(NO) 3 And V (n-butanol): v (absolute ethanol) =0.5-1.5:0.5-1.5.
Further, in the fourth step, the No. 2 coating solution includes: 8-12g/L H 2 IrCl 6 、8-12g/L RuCl 3 、3-6g/L SnCl 4· 5H 2 O、3-6g/L Mn(NO 3 ) 2 And V (n-butanol): v (absolute ethanol) =0.5-1.5:0.5-1.5.
Further, in the sixth step, the No. 3 coating solution includes: 12-16g/L H 2 IrCl 6 、12-16g/L RuCl 3 、8-12g/L Mn(NO 3 ) 2 And V (n-butanol): v (absolute ethanol) =0.5-1.5:0.5-1.5.
The gradient structure coating titanium anode has strong conductivity and corrosion resistance, and the groove voltage can be effectively reduced by introducing the Ti-Ag layer on the titanium substrate; snO (SnO) 2 Can refine coating grains, stabilize coating structure and reduce IrO 2 、RuO 2 Is used in the amount of (3); mnO (MnO) 2 The introduction of the composite material can be used as a porous framework material with large specific surface area, so that the coating structure is stabilized, the surface area of the coating is increased, and the number of surface sites of active substances is increased. RuO in oxide coating 2 -IrO 2 The content is gradually increased from inside to outside, the effective utilization rate of the active components is improved, the cost is reduced, the gradient structure can effectively slow down the stress mutation on the joint surface of the coating and the matrix, and the stability of the coating structure is improved.
The coating titanium anode prepared by the invention has low cell pressure and low electricity consumption in the zinc electrodeposition process, reduces the use amount of noble metal and controls the electrode cost. The service life of the titanium anode prepared by the method is 2 times that of the traditional anode, the cell voltage is reduced by more than 200mV, the direct current power consumption is reduced by 250kWh/t-Zn, and the direct economic benefit is that the power consumption cost is reduced by about 125 yuan/t-Zn.
The invention provides a coated titanium anode for zinc electrowinning, which comprises a titanium substrate, a Ti-Ag intermediate layer and IrO 2 -RuO 2 Ag transition layer and gradient method for preparing IrO 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]An active layer. Compared with the traditional Pb-Ag (1%) anode: intermediate layer of Ti-Ag and IrO 2 -RuO 2 The addition of the Ag transition layer improves the bonding force between the coating and the matrix and the conductivity of the matrix; the addition of Sn refines metal oxide particles, so that the utilization rate of noble metals is improved; mnO (MnO) 2 The introduction of the catalyst stabilizes the coating structure, increases the surface area of the coating, and improves the number of surface sites and corrosion resistance of active substances; the multi-layer gradient preparation process can improve the binding force between the active layers and reduce the manufacturing cost. The coated anode has good electrocatalytic performance and service life, has high oxygen evolution efficiency, high current efficiency and long service life in the zinc electrodeposition process, and is a better choice of anode materials for the zinc electrodeposition field.
Drawings
FIG. 1 is a schematic view of a structure of a coated titanium anode for zinc electrodeposition according to an embodiment of the present invention;
in the figure: (1) an intermediate layer; (2) a transition layer; (3) [ IrO 2 -RuO 2 -SnO 2 ] (1) An active layer; (4) [ IrO 2 -RuO 2 -MnO 2 ] (2) An active layer;
FIG. 2 is a schematic illustration of a coated titanium anode according to an embodiment of the present invention in a 0.5M sulfuric acid solution at 1A/cm 2 A polarization curve test result diagram under current density;
FIG. 3 is a schematic illustration of a coated titanium anode according to an embodiment of the present invention with 55g/L Zn in the electrolyte 2 SO 4 Solution with acidity of H 2 SO 4 165g/L, the temperature of the electrolytic tank is 38-40 ℃, the electrolytic time is 24 hours, and the flow rate of electrolyte is 470 mL/h;
FIG. 4 is a schematic illustration of a coated titanium anode according to an embodiment of the present invention in 1M sulfuric acid solution at 1A/cm 2 A graph of enhanced lifetime test results at current density;
FIG. 5 is a schematic view of a simplified device for electrochemical testing according to an embodiment of the present invention;
fig. 6 is a schematic structural diagram of a simple apparatus for zinc electrowinning according to an embodiment of the present invention.
Detailed Description
The invention is further described below with reference to examples and figures, but is not limited in any way, and any alterations or substitutions based on the teachings of the invention are within the scope of the invention.
The coated titanium anode for zinc electrodeposition comprises a titanium substrate, and further comprises an intermediate layer, a transition layer and a surface active layer;
the intermediate layer is Ti-Ag;
the transition layer is IrO 2 -RuO 2 -Ag；
The surface active layer is formed by IrO 2 、RuO 2 、SnO 2 、MnO 2 The surface active layer is divided into two layers, and the two layers are respectively [ IrO from inside to outside ] 2 -RuO 2 -SnO 2 ]，[IrO 2 -RuO 2 -MnO 2 ]。
The preparation method of the coated titanium anode for zinc electrodeposition comprises the following steps:
polishing, alkali washing and acid washing are carried out on a titanium substrate, and a Ti-Ag-containing intermediate layer titanium substrate is prepared by a chemical reduction method based on the treated titanium substrate;
step two, coating the coating liquid 1 on the titanium substrate containing the Ti-Ag intermediate layer obtained in the step one, and drying and roasting;
step three, repeating the step two for 3 times to obtain the intermediate layer containing Ti-Ag and IrO from inside to outside 2 -RuO 2 -a titanium substrate of an Ag transition layer;
step four, coating the coating liquid No. 2 on the titanium substrate in the step three, and drying and roasting;
step five, repeating the steps for 4 times to obtain the alloy containing Ti-Ag and IrO sequentially from inside to outside 2 -RuO 2 -Ag、[IrO 2 -RuO 2 -SnO 2 ]A coated titanium substrate;
step six, coating the coating liquid No. 3 on the titanium substrate obtained in the step five, and drying and roasting;
step seven, repeating the steps for six 5 times to obtain the alloy containing Ti-Ag and IrO from inside to outside 2 -RuO 2 -Ag、[IrO 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]A coated titanium anode;
the No. 1 coating liquid is as follows: 3-7g/L H 2 IrCl 6 、3-7g/L RuCl 3 、3-7g/L Ag(NO) 3 And V (n-butanol): v (absolute ethanol) =0.5-1.5:0.5-1.5;
the No. 2 coating liquid is as follows: 8-12g/L H 2 IrCl 6 、8-12g/L RuCl 3 、3-6g/L SnCl 4· 5H 2 O、3-6g/L Mn(NO 3 ) 2 And V (n-butanol): v (absolute ethanol) =0.5-1.5:0.5-1.5;
the No. 3 coating liquid is as follows: 12-16g/L H 2 IrCl 6 、12-16g/L RuCl 3 、8-12g/L Mn(NO 3 ) 2 And V (n-butanol): v (absolute ethanol) =0.5-1.5:0.5-1.5.
The preparation of the Ti-Ag-containing interlayer titanium substrate in the first step comprises the following steps:
(1) Polishing the surface of the titanium substrate, and performing alkaline cleaning, degreasing and etching for later use;
(2) Dropping ammonia water with the concentration of 70-90mL/L into 15-25g/L silver nitrate solution, clarifying the solution to obtain silver ammonia solution, and adding the silver ammonia solution into an equal volume of potassium sodium tartrate solution with the concentration of 90-110g/L to obtain silver plating solution;
(3) Placing the pretreated titanium plate into silver plating solution, standing for 1-1.5h at 20-35 ℃ to load a layer of uniform and compact simple substance Ag on the surface of the titanium plate, and obtaining the titanium substrate containing the Ti-Ag intermediate layer.
The present invention will be described in detail with reference to the accompanying drawings.
As shown in fig. 1, the coated titanium anode provided by the embodiment of the invention is sequentially provided with a titanium substrate, an intermediate layer, a transition layer and a surface active layer; the intermediate layer is Ti-Ag; the transition layer is IrO 2 -RuO 2 -Ag; the surface active layer is made of IrO 2 、RuO 2 、SnO 2 、MnO 2 The surface active layer is [ IrO from inside to outside 2 -RuO 2 -SnO 2 ]，[IrO 2 -RuO 2 -MnO 2 ]。
The preparation method of the coated titanium anode for zinc electrodeposition provided by the embodiment of the invention comprises the following steps:
1, polishing, alkali washing and acid washing a titanium substrate, and preparing a Ti-Ag-containing intermediate layer titanium substrate by a chemical reduction method based on the treated titanium substrate;
2, coating the coating liquid No. 1 on the titanium substrate containing the Ti-Ag intermediate layer obtained in the step one, drying for 10min at 120 ℃, and roasting for 20min at 450 ℃;
3, repeating the steps for 3 times to obtain the intermediate layer containing Ti-Ag and IrO from inside to outside 2 -RuO 2 -a titanium substrate of an Ag transition layer;
4, coating the No. 2 coating liquid on the titanium substrate in the third step, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 20min;
5, repeating the steps for 4 times to obtain the alloy containing Ti-Ag and IrO from inside to outside 2 -RuO 2 -Ag、[IrO 2 -RuO 2 -SnO 2 ]A coated titanium substrate;
6, coating the coating liquid No. 3 on the titanium substrate obtained in the step five, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 20min;
7, repeating the steps for six 5 times to obtain the alloy containing Ti-Ag and IrO from inside to outside 2 -RuO 2 -Ag、[IrO 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]A coated titanium anode;
the preparation method of the titanium substrate containing the Ti-Ag intermediate layer provided by the embodiment of the invention comprises the following steps:
(1) Polishing the surface of the titanium substrate, and then putting 5wt% of Na into the substrate 2 CO 3 Boiling in solution, alkali washing and degreasing for 0.5h, pickling in 10wt% boiling oxalic acid solution for 1.5h to remove surface oxide film, washing with tap water, deionized water and alcohol in sequence, and drying for later use;
(2) Dropping ammonia water (80 mL/L) into a silver nitrate solution (20 g/L), clarifying the solution to obtain a silver ammonia solution, and adding the silver ammonia solution into an equal volume of potassium sodium tartrate solution (100 g/L) to obtain silver plating solution;
(3) And (3) placing the pretreated titanium plate into silver plating solution, standing for 1h at a constant temperature of 30 ℃, and loading a layer of uniform and compact simple substance Ag on the surface of the titanium plate to obtain the titanium substrate containing the Ti-Ag intermediate layer.
The invention provides a preparation method of a titanium anode for zinc electrowinning coating, which is shown in figure 1, wherein the coating on the surface of a titanium substrate is respectively Ti-Ag and IrO from inside to outside 2 -RuO 2 -Ag、[IrO 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]；
The preparation method of the coated titanium anode for zinc electrodeposition provided by the invention comprises the following steps of;
step 1, polishing the surface of a titanium substrate, and then placing 5wt% of Na 2 CO 3 Boiling in solution, alkali washing and degreasing for 0.5h, pickling in 10wt% boiling oxalic acid solution for 1.5h to remove surface oxide film, washing with tap water, deionized water and alcohol in sequence, and drying for later use;
and 2, dropwise adding ammonia water (80 mL/L) into a silver nitrate solution (20 g/L), clarifying the solution to obtain a silver ammonia solution, and adding the silver ammonia solution into an equal volume of potassium sodium tartrate solution (100 g/L) to obtain silver plating solution.
And step 3, placing the pretreated titanium plate into silver plating solution, standing for 1h at a constant temperature of 30 ℃, and loading a layer of uniform and compact simple substance Ag on the surface of the titanium plate to obtain the titanium substrate containing the Ti-Ag intermediate layer.
Step 4, the solution containing 5g/L chloroiridic acid (H) 2 IrCl 6 ) 5g/L ruthenium trichloride (RuCl) 3 ) 5g/L silver nitrate (Ag (NO) 3 ) And V (n-butanol): v (absolute ethanol) =1:1, and drying at 120deg.C for 10min, baking at 450deg.C for 20min, and repeating the above steps for 3 times to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO sequentially from inside to outside 2 -RuO 2 -a titanium substrate of an Ag transition layer;
step 5, the solution containing 10g/L chloroiridic acid (H) 2 IrCl 6 ) 10g/L ruthenium trichloride (RuCl) 3 ) 5g/L tin tetrachloride (SnCl) 4· 5H 2 O), 5g/L manganese nitrate (Mn (NO) 3 ) 2 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on a Ti-Ag containing intermediate layer and IrO 2 -RuO 2 Repeating the above steps of coating, drying and roasting for 4 times on the titanium substrate of the Ag transition layer to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO sequentially from inside to outside 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ] (1) Is a titanium substrate;
step 6, the solution containing 15g/L chloroiridium acid (H) 2 IrCl 6 ) 15g/L ruthenium trichloride (RuCl) 3 ) 10g/L manganese nitrate (Mn (NO) 3 ) 2 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on the Ti-Ag containing intermediate layer, irO 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ] (1) Repeating the above steps for 5 times to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO from inside to outside 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]Is a titanium anode of (a).
As shown in fig. 3, curve a in fig. 3 represents a coated titanium anode for zinc electrodeposition prepared in accordance with the present invention; FIG. 3 is a graph b showing that the reinforced life of the conventional Pb-Ag anode is effectively improved, as shown in FIG. 3;
as shown in fig. 4, curve a in fig. 4 represents the oxygen evolution potential of the coated titanium anode prepared in accordance with the present invention; the chlorine evolution potential of the coated titanium anode prepared in accordance with the present invention is shown in curve b of fig. 4, and the oxygen-chlorine potential difference is shown to be greater than 200mV in fig. 4.
The invention is further illustrated by the following examples:
example 1
Step 1, polishing the surface of a titanium substrate, and then placing 5wt% of Na 2 CO 3 Boiling in solution, alkali washing and degreasing for 0.5h, pickling in 10wt% boiling oxalic acid solution for 1.5h to remove surface oxide film, washing with tap water, deionized water and alcohol in sequence, and drying for later use;
and 2, dropwise adding ammonia water (80 mL/L) into a silver nitrate solution (20 g/L), clarifying the solution to obtain a silver ammonia solution, and adding the silver ammonia solution into an equal volume of potassium sodium tartrate solution (100 g/L) to obtain silver plating solution.
And step 3, placing the pretreated titanium plate into silver plating solution, standing for 1h at a constant temperature of 30 ℃, and loading a layer of uniform and compact simple substance Ag on the surface of the titanium plate to obtain the titanium substrate containing the Ti-Ag intermediate layer.
Step 4, the solution containing 5g/L chloroiridic acid (H) 2 IrCl 6 ) 5g/L ruthenium trichloride (RuCl) 3 ) 5g/L silver nitrate (Ag (NO) 3 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on titanium containing Ti-Ag interlayerDrying the substrate at 120deg.C for 10min, baking at 450deg.C for 20min, and repeating the above steps for 3 times to obtain a substrate containing Ti-Ag interlayer and IrO sequentially from inside to outside 2 -RuO 2 -a titanium substrate of an Ag transition layer;
step 5, the solution containing 10g/L chloroiridic acid (H) 2 IrCl 6 ) 10g/L ruthenium trichloride (RuCl) 3 ) 5g/L tin tetrachloride (SnCl) 4· 5H 2 O), 5g/L manganese nitrate (Mn (NO) 3 ) 2 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on a Ti-Ag containing intermediate layer and IrO 2 -RuO 2 Repeating the above steps of coating, drying and roasting for 4 times on the titanium substrate of the Ag transition layer to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO sequentially from inside to outside 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ] (1) Is a titanium substrate;
step 6, the solution containing 15g/L chloroiridium acid (H) 2 IrCl 6 ) 15g/L ruthenium trichloride (RuCl) 3 ) 10g/L manganese nitrate (Mn (NO) 3 ) 2 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on the Ti-Ag containing intermediate layer, irO 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]Repeating the above steps for 5 times to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO from inside to outside 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]Is a titanium anode of (a). The obtained coated titanium anode is used in the zinc electrodeposition field.
Example 2
The preparation method of the coated titanium anode for zinc electrodeposition provided by the invention comprises the following steps of;
step 1, polishing the surface of a titanium substrate, and then placing 5wt% of Na 2 CO 3 Boiling in solution, alkali washing and degreasing for 0.5h, pickling in 10wt% boiling oxalic acid solution for 1.5h to remove surface oxide film, washing with tap water, deionized water and alcohol in sequence, and drying for later use;
and 2, dropwise adding ammonia water (80 mL/L) into a silver nitrate solution (20 g/L), clarifying the solution to obtain a silver ammonia solution, and adding the silver ammonia solution into an equal volume of potassium sodium tartrate solution (100 g/L) to obtain silver plating solution.
And step 3, placing the pretreated titanium plate into silver plating solution, standing for 1h at a constant temperature of 30 ℃, and loading a layer of uniform and compact simple substance Ag on the surface of the titanium plate to obtain the titanium substrate containing the Ti-Ag intermediate layer.
Step 4, the solution containing 5g/L chloroiridic acid (H) 2 IrCl 6 ) 5g/L ruthenium trichloride (RuCl) 3 ) 5g/L silver nitrate (Ag (NO) 3 ) And V (n-butanol): v (absolute ethanol) =1:1, and drying at 120deg.C for 10min, baking at 450deg.C for 20min, and repeating the above steps for 3 times to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO sequentially from inside to outside 2 -RuO 2 -a titanium substrate of an Ag transition layer;
step 5, the solution containing 10g/L chloroiridic acid (H) 2 IrCl 6 ) 10g/L ruthenium trichloride (RuCl) 3 ) 5g/L tin tetrachloride (SnCl) 4· 5H 2 O), 5g/L manganese nitrate (Mn (NO) 3 ) 2 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on a Ti-Ag containing intermediate layer and IrO 2 -RuO 2 Repeating the above steps of coating, drying and roasting for 4 times on the titanium substrate of the Ag transition layer to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO sequentially from inside to outside 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]Is a titanium substrate;
step 6, the solution containing 15g/L chloroiridium acid (H) 2 IrCl 6 ) 15g/L ruthenium trichloride (RuCl) 3 ) 10g/L manganese nitrate (Mn (NO) 3 ) 2 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on the Ti-Ag containing intermediate layer, irO 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]Repeating the above steps for 5 times to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO from inside to outside 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]Is a titanium anode of (a). The obtained coated titanium anode is used in the zinc electrodeposition field.
Example 3
The preparation method of the coated titanium anode for zinc electrodeposition provided by the invention comprises the following steps of;
step 1, polishing the surface of a titanium substrate, and then placing 5wt% of Na 2 CO 3 Boiling in solution, alkali washing and degreasing for 0.5h, pickling in 10wt% boiling oxalic acid solution for 1.5h to remove surface oxide film, washing with tap water, deionized water and alcohol in sequence, and drying for later use;
and 2, dropwise adding ammonia water (80 mL/L) into a silver nitrate solution (20 g/L), clarifying the solution to obtain a silver ammonia solution, and adding the silver ammonia solution into an equal volume of potassium sodium tartrate solution (100 g/L) to obtain silver plating solution.
And step 3, placing the pretreated titanium plate into silver plating solution, standing for 1h at a constant temperature of 30 ℃, and loading a layer of uniform and compact simple substance Ag on the surface of the titanium plate to obtain the titanium substrate containing the Ti-Ag intermediate layer.
Step 4, the solution containing 5g/L chloroiridic acid (H) 2 IrCl 6 ) 5g/L ruthenium trichloride (RuCl) 3 ) 5g/L silver nitrate (Ag (NO) 3 ) And V (n-butanol): v (absolute ethanol) =1:1, and drying at 120deg.C for 10min, baking at 450deg.C for 20min, and repeating the above steps for 3 times to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO sequentially from inside to outside 2 -RuO 2 -a titanium substrate of an Ag transition layer;
step 5, the solution containing 10g/L chloroiridic acid (H) 2 IrCl 6 ) 10g/L ruthenium trichloride (RuCl) 3 ) 5g/L tin tetrachloride (SnCl) 4· 5H 2 O), 5g/L manganese nitrate (Mn (NO) 3 ) 2 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on a Ti-Ag containing intermediate layer and IrO 2 -RuO 2 Repeating the above-mentioned coating-drying on the titanium substrate of the Ag transition layerDrying-roasting for 4 times to obtain the intermediate layer containing Ti-Ag and IrO from inside to outside 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]Is a titanium substrate;
step 6, the solution containing 15g/L chloroiridium acid (H) 2 IrCl 6 ) 15g/L ruthenium trichloride (RuCl) 3 ) 10g/L manganese nitrate (Mn (NO) 3 ) 2 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on the Ti-Ag containing intermediate layer, irO 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]Repeating the above steps for 5 times to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO from inside to outside 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]Is a titanium anode of (a). The obtained coated titanium anode is used in the zinc electrodeposition field.
Example 4
The preparation method of the coated titanium anode for zinc electrodeposition provided by the invention comprises the following steps of;
step 1, polishing the surface of a titanium substrate, and then placing 5wt% of Na 2 CO 3 Boiling in solution, alkali washing and degreasing for 0.5h, pickling in 10wt% boiling oxalic acid solution for 1.5h to remove surface oxide film, washing with tap water, deionized water and alcohol in sequence, and drying for later use;
and 2, dropwise adding ammonia water (80 mL/L) into a silver nitrate solution (20 g/L), clarifying the solution to obtain a silver ammonia solution, and adding the silver ammonia solution into an equal volume of potassium sodium tartrate solution (100 g/L) to obtain silver plating solution.
And step 3, placing the pretreated titanium plate into silver plating solution, standing for 1h at a constant temperature of 30 ℃, and loading a layer of uniform and compact simple substance Ag on the surface of the titanium plate to obtain the titanium substrate containing the Ti-Ag intermediate layer.
Step 4, the solution containing 5g/L chloroiridic acid (H) 2 IrCl 6 ) 5g/L ruthenium trichloride (RuCl) 3 ) 5g/L silver nitrate (Ag (NO) 3 ) And V (n-butanol): v (Anhydrous B)Alcohol) =1:1, is coated on a titanium substrate containing a Ti-Ag interlayer, dried at 120 ℃ for 10min, baked at 450 ℃ for 20min, and the coating-drying-baking is repeated for 3 times to obtain a titanium substrate containing a Ti-Ag interlayer and IrO in sequence from inside to outside 2 -RuO 2 -a titanium substrate of an Ag transition layer;
step 5, the solution containing 10g/L chloroiridic acid (H) 2 IrCl 6 ) 10g/L ruthenium trichloride (RuCl) 3 ) 5g/L tin tetrachloride (SnCl) 4· 5H 2 O), 5g/L manganese nitrate (Mn (NO) 3 ) 2 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on a Ti-Ag containing intermediate layer and IrO 2 -RuO 2 Repeating the above steps of coating, drying and roasting for 4 times on the titanium substrate of the Ag transition layer to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO sequentially from inside to outside 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]Is a titanium substrate;
step 6, the solution containing 15g/L chloroiridium acid (H) 2 IrCl 6 ) 15g/L ruthenium trichloride (RuCl) 3 ) 10g/L manganese nitrate (Mn (NO) 3 ) 2 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on the Ti-Ag containing intermediate layer, irO 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]Repeating the above steps for 5 times to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO from inside to outside 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]Is a titanium anode of (a). The obtained coated titanium anode is used in the zinc electrodeposition field.
Example 5
The preparation method of the coated titanium anode for zinc electrodeposition provided by the invention comprises the following steps of;
step 1, polishing the surface of a titanium substrate, and then placing 5wt% of Na 2 CO 3 Boiling in solution, alkali washing to remove oil for 0.5h, pickling in 10wt% boiling oxalic acid solution for 1.5h to remove surface oxide film, sequentially adding tap water and deionized waterAnd alcohol cleaning and drying for later use;
and 2, dropwise adding ammonia water (80 mL/L) into a silver nitrate solution (20 g/L), clarifying the solution to obtain a silver ammonia solution, and adding the silver ammonia solution into an equal volume of potassium sodium tartrate solution (100 g/L) to obtain silver plating solution.
And step 3, placing the pretreated titanium plate into silver plating solution, standing for 1h at a constant temperature of 30 ℃, and loading a layer of uniform and compact simple substance Ag on the surface of the titanium plate to obtain the titanium substrate containing the Ti-Ag intermediate layer.
Step 4, the solution containing 5g/L chloroiridic acid (H) 2 IrCl 6 ) 5g/L ruthenium trichloride (RuCl) 3 ) 5g/L silver nitrate (Ag (NO) 3 ) And V (n-butanol): v (absolute ethanol) =1:1, and drying at 120deg.C for 10min, baking at 450deg.C for 20min, and repeating the above steps for 3 times to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO sequentially from inside to outside 2 -RuO 2 -a titanium substrate of an Ag transition layer;
step 5, the solution containing 10g/L chloroiridic acid (H) 2 IrCl 6 ) 10g/L ruthenium trichloride (RuCl) 3 ) 5g/L tin tetrachloride (SnCl) 4· 5H 2 O), 5g/L manganese nitrate (Mn (NO) 3 ) 2 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on a Ti-Ag containing intermediate layer and IrO 2 -RuO 2 Repeating the above steps of coating, drying and roasting for 4 times on the titanium substrate of the Ag transition layer to obtain a titanium substrate containing Ti-Ag intermediate layer and IrO sequentially from inside to outside 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]Is a titanium substrate;
step 6, the solution containing 15g/L chloroiridium acid (H) 2 IrCl 6 ) 15g/L ruthenium trichloride (RuCl) 3 ) 10g/L manganese nitrate (Mn (NO) 3 ) 2 ) And V (n-butanol): v (absolute ethanol) =1:1 mixed solution was coated on the Ti-Ag containing intermediate layer, irO 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ] (1) Repeating the above-mentioned coating-drying-firing for 5 times on the titanium substrateObtaining the intermediate layer containing Ti-Ag and IrO from inside to outside 2 -RuO 2 Ag transition layer and surface active layer [ IrO ] 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]Is a titanium anode of (a). The obtained coated titanium anode is used in the zinc electrodeposition field.
Performance testing
The electrochemical treatment performance test is carried out on the coated titanium anode prepared in the embodiment 1-5 of the invention, and the method comprises the following steps: cutting four 1cm x 1cm anode samples of the prepared coating, and inserting the first sample, the titanium sheet cathode and the saturated calomel electrode into an electrolytic cell containing 0.5M sulfuric acid solution; the second part and the cathode of the titanium sheet are inserted into an electrolytic cell containing 1M sulfuric acid solution, and a reinforced life test experiment (the electrode is regarded as invalid when the cell pressure is increased by 10V compared with the initial stage) is carried out by a direct current power supply, the temperature of the electrolyte is 30 ℃, and the anode current density is 20000A/M 2 Electrolytic 1h postharvest
The electrolyte sulfuric acid concentration was measured by chemical analysis (oxygen evolution efficiency was calculated). The method comprises the steps of carrying out a first treatment on the surface of the Third portion and aluminum cathode insert containing 55g/L Zn 2 SO 4 Solution with acidity of H 2 SO 4 In 165g/L electrolyte, the temperature of an electrolytic tank is 38-40 ℃, the electrowinning time is 24h, the flow rate of the electrolyte is 470mL/h, a direct current power supply constant current is adopted to carry out zinc electrowinning experiment, and the anode current density is 10000A/m 2 The anode current efficiency is calculated by the formula (1).
（1）
Wherein: η (eta) i Represents cathode current efficiency,%; m represents the actual yield of zinc precipitated in the time t, g; i represents the current passing between the cathode and the anode, A; t represents the electrodeposition time, h; n represents the number of cells; q zinc electrochemical equivalent, 1.220 g/(a·h).
The results of the electrochemical performance test and the enhanced lifetime test are shown in table 1; the results of the zinc electrowinning experiments are shown in table 2.
TABLE 1 results of electrochemical Performance test of coated titanium anodes
As can be seen from Table 1, the oxygen evolution potential of the titanium anode with five coatings prepared by the method is approximately 200mV lower than that of the conventional Pb-Ag (1%) anode, the strengthening service life is more than 140h, and the oxygen evolution efficiency is more than 90%. All three important parameters are better than the traditional Pb-Ag (1%) anode, which shows that the coated titanium anode prepared by the invention has advantages in the application of electrodeposited zinc.
TABLE 2 results of titanium anode electrodeposited Zinc energy test for coating
As can be seen from Table 2, the five coated titanium anodes prepared by the method of the invention have low cell pressure, small variation and high current efficiency in the zinc electrodeposition process, and the two important parameters are better than those of the traditional Pb-Ag (1%) anode. The coating titanium anode prepared by the invention has good electrochemical performance in the zinc electrowinning process.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (2)
1. The preparation method of the coated titanium anode for zinc electrodeposition comprises a titanium substrate, and is characterized by further comprising an intermediate layer, a transition layer and a surface active layer;
the intermediate layer is Ti-Ag;
the transition layer is IrO 2 -RuO 2 -Ag；
The surface active layer is formed by IrO 2 、RuO 2 、SnO 2 、MnO 2 The surface active layer is divided into two layers from inside to outsideIs not [ IrO ] 2 -RuO 2 -SnO 2 ]，[IrO 2 -RuO 2 -MnO 2 ]；
The preparation method comprises the following steps:
polishing, alkali washing and acid washing are carried out on a titanium substrate, and a Ti-Ag-containing intermediate layer titanium substrate is prepared by a chemical reduction method based on the treated titanium substrate;
step two, coating the coating liquid 1 on the titanium substrate containing the Ti-Ag intermediate layer obtained in the step one, and drying and roasting;
step three, repeating the step two for 3 times to obtain the intermediate layer containing Ti-Ag and IrO from inside to outside 2 -RuO 2 -a titanium substrate of an Ag transition layer;
step four, coating the coating liquid No. 2 on the titanium substrate in the step three, and drying and roasting;
step five, repeating the steps for 4 times to obtain the alloy containing Ti-Ag and IrO sequentially from inside to outside 2 -RuO 2 -Ag、[IrO 2 -RuO 2 -SnO 2 ]A coated titanium substrate;
step six, coating the coating liquid No. 3 on the titanium substrate obtained in the step five, and drying and roasting;
step seven, repeating the steps for six 5 times to obtain the alloy containing Ti-Ag and IrO from inside to outside 2 -RuO 2 -Ag、[IrO 2 -RuO 2 -SnO 2 ]、[IrO 2 -RuO 2 -MnO 2 ]A coated titanium anode;
the No. 1 coating liquid is as follows: 3-7g/L H 2 IrCl 6 、3-7g/L RuCl 3 、3-7g/L Ag(NO) 3 And V n-butanol: v absolute ethanol = 0.5-1.5:0.5-1.5 mixed solution;
the No. 2 coating liquid is as follows: 8-12g/L H 2 IrCl 6 、8-12g/L RuCl 3 、3-6g/L SnCl 4 ×5H 2 O、3-6g/L Mn(NO 3 ) 2 And V n-butanol: v absolute ethanol = 0.5-1.5:0.5-1.5 mixed solution;
the No. 3 coating liquid is as follows: 12-16g/L H 2 IrCl 6 、12-16g/L RuCl 3 、8-12g/L Mn(NO 3 ) 2 And V n-butanol: v anhydrousEthanol=0.5-1.5:0.5-1.5.
2. The method of claim 1, wherein the preparing the Ti-Ag containing interlayer titanium substrate in step one comprises the steps of:
(1) Polishing the surface of the titanium substrate, and performing alkaline cleaning, degreasing and etching for later use;
(2) Dropping ammonia water with the concentration of 70-90mL/L into 15-25g/L silver nitrate solution, clarifying the solution to obtain silver ammonia solution, and adding the silver ammonia solution into an equal volume of potassium sodium tartrate solution with the concentration of 90-110g/L to obtain silver plating solution;
(3) Placing the pretreated titanium plate into silver plating solution, standing for 1-1.5h at 20-35 ℃ to load a layer of uniform and compact simple substance Ag on the surface of the titanium plate, and obtaining the titanium substrate containing the Ti-Ag intermediate layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210218316.2A CN114457368B (en) | 2022-03-08 | 2022-03-08 | Coated titanium anode for zinc electrodeposition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210218316.2A CN114457368B (en) | 2022-03-08 | 2022-03-08 | Coated titanium anode for zinc electrodeposition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114457368A CN114457368A (en) | 2022-05-10 |
| CN114457368B true CN114457368B (en) | 2023-11-21 |
Family
ID=81418422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210218316.2A Active CN114457368B (en) | 2022-03-08 | 2022-03-08 | Coated titanium anode for zinc electrodeposition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114457368B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3234110A (en) * | 1959-02-06 | 1966-02-08 | Amalgamated Curacao Patents Co | Electrode and method of making same |
| CN101880891A (en) * | 2010-04-13 | 2010-11-10 | 大连理工大学 | High-stability DSA anode for preparing chlorine by electrolysis and preparation method thereof |
| CN108149280A (en) * | 2017-12-20 | 2018-06-12 | 西安泰金工业电化学技术有限公司 | A kind of swirl electrolysis device compound lead anode of titanium-based pipe network and preparation method thereof |
| CN109023436A (en) * | 2018-07-23 | 2018-12-18 | 昆明理工大学 | A kind of titanium-based β-MnO2-RuO2Composite coating anode plate and the preparation method and application thereof |
| CN112195482A (en) * | 2020-10-15 | 2021-01-08 | 昆明冶金研究院有限公司 | Composite titanium anode plate and preparation method thereof |
| CN113800606A (en) * | 2021-08-28 | 2021-12-17 | 西安电子科技大学 | Coating titanium anode for treatment of circulating cooling water, preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010043085A1 (en) * | 2010-10-28 | 2012-05-03 | Bayer Materialscience Aktiengesellschaft | Electrode for electrolytic chlorine production |
-
2022
- 2022-03-08 CN CN202210218316.2A patent/CN114457368B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3234110A (en) * | 1959-02-06 | 1966-02-08 | Amalgamated Curacao Patents Co | Electrode and method of making same |
| CN101880891A (en) * | 2010-04-13 | 2010-11-10 | 大连理工大学 | High-stability DSA anode for preparing chlorine by electrolysis and preparation method thereof |
| CN108149280A (en) * | 2017-12-20 | 2018-06-12 | 西安泰金工业电化学技术有限公司 | A kind of swirl electrolysis device compound lead anode of titanium-based pipe network and preparation method thereof |
| CN109023436A (en) * | 2018-07-23 | 2018-12-18 | 昆明理工大学 | A kind of titanium-based β-MnO2-RuO2Composite coating anode plate and the preparation method and application thereof |
| CN112195482A (en) * | 2020-10-15 | 2021-01-08 | 昆明冶金研究院有限公司 | Composite titanium anode plate and preparation method thereof |
| CN113800606A (en) * | 2021-08-28 | 2021-12-17 | 西安电子科技大学 | Coating titanium anode for treatment of circulating cooling water, preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| "Electrochemical oxidation of aniline using Ti/RuO2-SnO2 and Ti/RuO2-IrO2 as anode";Zhu, Xu 等;《CHEMOSPHERE》;第269卷;文献号 128734 * |
| "IrO2-MnO2中间层Ti/RuO2-TiO2-SnO2电极制备及性能";刘晓军 等;《稀有金属材料与工程》;第54-57页 * |
| "Ti/IrO2-RuO2-SnO2阳极的制备与性能研究";庄晓东 等;《现代化工》;第145-149页 * |
| "锌电积工艺中新型阳极的研究进展";牛永胜 等;《热加工工艺》;第26-30、35页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114457368A (en) | 2022-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2644721B1 (en) | Method for producing highly corrosion-resistant porous Ni-Sn body | |
| Chen et al. | Corrosion resistance mechanism of a novel porous Ti/Sn-Sb-RuOx/β-PbO2 anode for zinc electrowinning | |
| Yang et al. | Effects of manganese nitrate concentration on the performance of an aluminum substrate β-PbO2–MnO2–WC–ZrO2 composite electrode material | |
| CN106283125A (en) | Metal electro-deposition coated titanium electrode and preparation method thereof | |
| US20090293262A1 (en) | Bipolar plate for fuel cell and method for manufacturing same | |
| JP4673628B2 (en) | Cathode for hydrogen generation | |
| CN113690455B (en) | Long-life anode electrode material and preparation method thereof | |
| Yang et al. | Effects of current density on preparation and performance of Al/conductive coating/a-PbO2-CeO2-TiO2/ß-PbO2-MnO2-WC-ZrO2 composite electrode materials | |
| CN106048690B (en) | A kind of titanium-based titanium dioxide nanotube composite anode and preparation method thereof | |
| CN113800606B (en) | Coating titanium anode for treatment of circulating cooling water, preparation method and application | |
| CN106086989B (en) | A kind of titania modified by Argentine nanotube composite anode and preparation method thereof | |
| CN111634980A (en) | Conductive support material of electrode plate for lithium extraction by electrochemical de-intercalation method | |
| CN106835193B (en) | A kind of Pb bases/3D-PbO2/MeOx composite anodes and preparation method thereof | |
| CN112195482B (en) | Composite titanium anode plate and preparation method thereof | |
| CN109628957A (en) | A kind of preparation method of Zinc electrolysis titanium-based nano composite anode | |
| US6368489B1 (en) | Copper electrowinning | |
| US6231731B1 (en) | Electrolyzing electrode and process for the production thereof | |
| CN114457368B (en) | Coated titanium anode for zinc electrodeposition and preparation method thereof | |
| EP0046449A1 (en) | Dimensionally stable coated electrode for electrolytic process, comprising protective oxide interface on valve metal base, and process for its manufacture | |
| CN106521610B (en) | A kind of hexavalent chromium plating combination Ni―Ti anode and preparation method thereof | |
| CN108060451B (en) | Preparation method of hydrophobic natural fiber composite lead dioxide anode | |
| Pavlović et al. | On the use of platinized and activated titanium anodes in some electrodeposition processes | |
| CN114164419B (en) | Method for preparing platinum active layer on anode plate by thermal decomposition method | |
| CN101619466A (en) | Load type multi-element oxygen-separating catalyst and preparation method thereof | |
| CN112573626A (en) | Titanium electrode and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |