CN117026313A - Method for producing anode for electrolysis and anode for electrolysis - Google Patents
Method for producing anode for electrolysis and anode for electrolysis Download PDFInfo
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- CN117026313A CN117026313A CN202310218182.9A CN202310218182A CN117026313A CN 117026313 A CN117026313 A CN 117026313A CN 202310218182 A CN202310218182 A CN 202310218182A CN 117026313 A CN117026313 A CN 117026313A
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000000758 substrate Substances 0.000 claims abstract description 72
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000010936 titanium Substances 0.000 claims abstract description 64
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 64
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000005530 etching Methods 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 238000005488 sandblasting Methods 0.000 claims abstract description 6
- 238000012937 correction Methods 0.000 claims abstract description 5
- 238000005238 degreasing Methods 0.000 claims abstract description 5
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 16
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052741 iridium Inorganic materials 0.000 claims description 14
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 8
- 239000003049 inorganic solvent Substances 0.000 claims description 7
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 230000001680 brushing effect Effects 0.000 claims description 4
- -1 butanediol tantalum Chemical compound 0.000 claims description 4
- RNEYMQMZICKRTG-UHFFFAOYSA-I Cl.[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Ta+5] Chemical compound Cl.[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Ta+5] RNEYMQMZICKRTG-UHFFFAOYSA-I 0.000 claims description 3
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 claims description 3
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 3
- 238000007590 electrostatic spraying Methods 0.000 claims description 3
- JVOQKOIQWNPOMI-UHFFFAOYSA-N ethanol;tantalum Chemical compound [Ta].CCO JVOQKOIQWNPOMI-UHFFFAOYSA-N 0.000 claims description 3
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 claims description 3
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 claims description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 5
- 230000002035 prolonged effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000276425 Xiphophorus maculatus Species 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- SMVPNBSENDTIEH-UHFFFAOYSA-M [Ir]Br Chemical compound [Ir]Br SMVPNBSENDTIEH-UHFFFAOYSA-M 0.000 description 1
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 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
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The application discloses a preparation method of an anode for electrolysis and the anode for electrolysis, wherein the method comprises the following steps: selecting a titanium substrate as an anode substrate; the titanium substrate is of a net-shaped structure or a plate-shaped structure, and the thickness is 0.1-8 mm; carrying out surface pretreatment on the titanium substrate, wherein the surface pretreatment at least comprises surface degreasing, sand blasting and shape correction; acid etching is carried out on the titanium substrate; wherein the acid etching treatment comprises soaking for 1-2.5 hours by 5-18% hydrochloric acid, or boiling for 2-6 hours by 7-15% oxalic acid, or boiling for 1-4 hours by 10-20% sulfuric acid; cleaning and drying the titanium substrate; and (3) coating a catalyst coating on the titanium substrate after the drying treatment until the catalyst coating reaches a set coating amount.
Description
Technical Field
The application relates to an electrode manufacturing technology of an electrolytic tank, in particular to a preparation method of an anode for electrolysis and the anode for electrolysis.
Background
Dimensionally stable anode (Dimensionally Stable Anode, DSA) electrodes are often used in chlorine, hydrogen and oxygen evolution electrolysis environments, and particularly in the electrolytic copper foil industry in recent years. The electrolytic copper foil is an important material for manufacturing copper-clad plates, printed circuit boards and lithium ion batteries. The anode material is one of the most critical components in electrolytic copper foil production equipment, and the anode material is subjected to a series of transition from a soluble anode, a lead anode and the like to the current noble metal catalyst DSA titanium anode with more excellent service performance, higher electrolysis efficiency and no pollution in order to continuously adapt to the requirements of electrolytic copper foil products. The thickness of the electrolytic copper foil is required to be thinner and thinner, so that the running current density of the anode is increased continuously, the requirement on the anode is also higher and higher, and meanwhile, the anode potential has direct influence on the electric energy efficiency and the copper foil cost in the electrolytic process. Under the working condition of high current density, oxygen permeation easily occurs in the anode, so that the catalyst is consumed and deactivated, the titanium substrate is oxidized, and the anode is disabled.
Disclosure of Invention
In view of the foregoing, the present application provides a method for producing an anode for electrolysis and an anode for electrolysis, which can solve at least the above-mentioned problems.
In a first aspect, the present application provides a method for preparing an anode for electrolysis, comprising:
selecting a titanium substrate as an anode substrate; the titanium substrate is of a net-shaped structure or a plate-shaped structure, and the thickness is 0.1-8 mm;
carrying out surface pretreatment on the titanium substrate, wherein the surface pretreatment at least comprises surface degreasing, sand blasting and shape correction;
acid etching is carried out on the titanium substrate; wherein the acid etching treatment comprises soaking for 1-2.5 hours by 5-18% hydrochloric acid, or boiling for 2-6 hours by 7-15% oxalic acid, or boiling for 1-4 hours by 10-20% sulfuric acid;
cleaning and drying the titanium substrate;
and (3) coating a catalyst coating on the titanium substrate after the drying treatment until the catalyst coating reaches a set coating amount.
In some embodiments, the catalyst coating is configured by:
iridium and tantalum are mixed according to the following proportion of (5-80): (5 to 50) in a molar ratio in an organic solvent or an inorganic solvent as a coating solution of the catalyst coated on the titanium substrate.
In some embodiments, the organic solvent comprises one or a mixture of two of n-butanol, isopropanol, ethanol.
In some embodiments, the inorganic solvent comprises a hydrochloric acid solution.
In some embodiments, the iridium and tantalum are mixed according to (5-80): the molar ratio of (5-50) is mixed in an organic solvent or an inorganic solvent, comprising:
any one of iridium tetrachloride, iridium trichloride, chloroiridic acid, bromoiridic acid and iridium acetate is selected;
any one of tantalum chloride hydrochloric acid solution, n-butyl alcohol tantalum solution, ethanol tantalum and butanediol tantalum is selected;
the iridium solution and the tantalum solution are selected, so that the molar ratio of iridium to tantalum is (5-80): the section of (5) to (50), a catalyst coating layer is formed.
In some embodiments, said applying a catalyst coating to said titanium substrate after said drying treatment until said catalyst coating reaches a set application amount comprises:
uniformly brushing the catalyst coating solution on the titanium substrate after the drying treatment by a mechanical brushing mode and an electrostatic spraying mode, drying, then implanting the titanium substrate into a high-temperature furnace for burning, keeping the temperature at 440-550 ℃, preserving the heat for 10-90 minutes, and repeating the coating process after cooling until the catalyst coating reaches the preset coating amount.
In some embodiments, the mesh substrate comprises a cell plate mesh, a woven mesh; the thickness of the mesh-shaped base material is preferably 0.3 to 2mm.
In some embodiments, the thickness of the plate-like substrate is preferably 1 to 7mm.
In a second aspect of the embodiment of the present application, an anode for electrolysis is provided, and the anode for electrolysis is prepared by using the anode preparation method for electrolysis.
According to the technical scheme, the titanium substrate is subjected to acid etching treatment, so that corresponding corrosion small holes are formed in the titanium substrate, and a catalyst coating is coated on the corroded titanium substrate, namely, the metallic elements iridium and tantalum are coated on the titanium substrate, and are uniformly distributed on the surface of the titanium substrate, so that a protective layer is well formed, the service life of the electrode is prolonged, the electrolytic voltage is reduced, the electrolytic copper foil anode is particularly suitable for an electrolytic copper foil anode, the service life of a related DSA anode is prolonged, lower electrolytic energy consumption is obtained, and the electrolytic efficiency is improved.
The foregoing description is only an overview of the present application, and is intended to be implemented in accordance with the teachings of the present application in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present application more readily apparent.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Also, like reference numerals are used to designate like parts throughout the accompanying drawings. In the drawings:
FIG. 1 shows an enlarged schematic view of an anode microscope for electrolysis according to an embodiment of the present application;
FIG. 2 shows an enlarged schematic view of an anode microscope for electrolysis according to an embodiment of the present application;
fig. 3 shows a schematic diagram of the service life of the electrolytic anode strengthening treatment according to the embodiment of the application.
Detailed Description
Embodiments of the technical scheme of the present application will be described in detail below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present application, and thus are merely examples, and are not intended to limit the scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having" and any variations thereof in the description of the application and the claims and the description of the drawings above are intended to cover a non-exclusive inclusion.
In the description of embodiments of the present application, the technical terms "first," "second," and the like are used merely to distinguish between different objects and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated, a particular order or a primary or secondary relationship. In the description of the embodiments of the present application, the meaning of "plurality" is two or more unless explicitly defined otherwise.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
In the description of the embodiments of the present application, the term "and/or" is merely an association relationship describing an association object, and indicates that three relationships may exist, for example, a and/or B may indicate: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
In the description of the embodiments of the present application, the term "plurality" means two or more (including two), and similarly, "plural sets" means two or more (including two), and "plural sheets" means two or more (including two).
In the description of the embodiments of the present application, the orientation or positional relationship indicated by the technical terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. are based on the orientation or positional relationship shown in the drawings, and are merely for convenience of description and simplification of the description, and do not indicate or imply that the apparatus or element referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the embodiments of the present application.
In the description of the embodiments of the present application, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured" and the like should be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally formed; or may be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the embodiments of the present application will be understood by those of ordinary skill in the art according to specific circumstances.
According to the DSA anode provided by the embodiment of the application, the titanium substrate is adopted as the substrate, the iridium (Ir) metal and the tantalum (Ta) metal are coated on the surface of the titanium substrate to form the protective layer of the DSA anode, and the coating of the Ir-Ta component with the corresponding layer thickness is arranged, so that the anode has good catalytic activity, long service life and low coating cost.
The preparation method of the DSA anode provided by the embodiment of the application comprises the following steps:
titanium base materials are selected as preparation base materials for the anode of the embodiment of the application; the substrate comprises a reticular substrate and a platy substrate, the thickness of the reticular substrate is 0.1-8 mm, the reticular titanium substrate can be a porous platy net or a woven net, and the thickness is preferably 0.3-2 mm; the thickness of the plate-like base material is preferably 1 to 7mm.
The surface of the titanium substrate is correspondingly pretreated, and the pretreatment mainly comprises the following steps:
and (3) carrying out oil removal treatment, sand blasting treatment and shape correction treatment on the surface of the titanium substrate.
Here, degreasing is a treatment process of oil-separating oil-containing substances on the surface of a titanium substrate and removing grease from the surface of the titanium substrate. The degreasing treatment of the surface of the titanium substrate can be achieved by coating benzene, ethers, ketones, phenols, chlorine-containing solvents, etc., or by coating trichloroethane, trichloroethylene, perchloroethylene, etc., on the surface of the titanium substrate.
Compressed air with the pressure not exceeding 0.8MPa is used as a power source for sand blasting to form high-speed spray beams (copper ore sand, quartz sand, silicon carbide, iron sand and sea sand), and the high-speed spray beams are sprayed onto the surface of the titanium substrate, so that the appearance or shape of the surface of the titanium substrate is changed. Due to the impact and cutting action of the abrasive on the surface of the titanium substrate, the surface of the titanium substrate obtains corresponding cleanliness and different roughness, so that the mechanical property of the surface of the titanium substrate is improved, and the adhesive force between the surface of the titanium substrate and the coating is increased.
And (3) performing shape correction treatment on the titanium base material subjected to sand blasting treatment, so that the size and shape of the titanium base material can meet the basic structural requirement of the anode.
In the embodiment of the application, before the titanium substrate is coated with the catalyst coating, the titanium substrate is also subjected to acid etching treatment, and as one implementation way, the acid etching treatment comprises soaking the titanium substrate in 5-18% hydrochloric acid for 1-2.5 hours, boiling the titanium substrate in 7-15% oxalic acid for 2-6 hours, or boiling the titanium substrate in 10-20% sulfuric acid for 1-4 hours.
In the embodiment of the application, the titanium substrate is cleaned and dried before the titanium substrate is coated with the catalyst coating. The washing may be performed with distilled water or the like.
In the embodiment of the application, the preparation of the catalyst coating is also needed, and the specific mode is as follows:
the iridium source is any one of iridium tetrachloride, iridium trichloride, chloroiridium acid, bromoiridium acid and iridium acetate;
the tantalum source is any one of tantalum chloride hydrochloric acid solution, n-butyl alcohol tantalum solution, ethanol tantalum and butanediol tantalum;
further mixing the raw materials into a solution, wherein the solvent can be selected from organic solvents, and can be one or two of n-butanol, isopropanol and ethanol; alternatively, the inorganic solvent may be aqueous hydrochloric acid. The iridium raw material comprises the following components: tantalum= (5-80): (5-50) molar ratio.
The mixed catalyst solution is uniformly coated on a pretreated titanium (net or plate) substrate in a fractional and uniform way by adopting the modes of manual coating, mechanical coating, electrostatic spraying and the like, and is put into a high-temperature furnace for burning at 440-550 ℃ after being dried, kept for 10-90 minutes, cooled and the process is repeated until the preset coating amount is reached.
As shown in fig. 1 and 2, the microstructure of the anode for the electrode is greatly changed by the treatment of the embodiment of the application, the mechanical properties of the titanium substrate are also changed essentially, and the elastic modulus, the yield strength, the tensile strength and the like are obviously improved. Mainly due to grain refinement and high density dislocation.
Carrying out life-strengthening electrolysis experiment on the electrode after coating, and carrying out life-strengthening electrolysis experiment on the electrode in electrolyte H 2 SO 4 The current density is 30KA/m 2 The test piece in the experimental condition of example 4 has the longest electrolysis time, the voltage of the test piece is far lower than that of other test pieces, and the voltage is stable in the electrolysis process.
In the presence of H as electrolyte 2 SO 4 The current density is 30KA/m 2 The results of the enhanced lifetime test of the electrodes prepared by the preparation method provided by the embodiment of the present application under the electrolysis conditions are shown in fig. 3. As can be seen from fig. 3, the electrode sample prepared by the preparation method according to the embodiment of the application has an electrolysis time as long as 1200h, and can obtain a longer anode life and a lower voltage; the electrode prepared by the embodiment of the application has the advantages of high density of iridium-tantalum crystals, fine grain size, dense active sites in the reaction process, microscopic cracks on the surface of the electrode, larger specific surface area, voltage reduction in the electrolysis process and prolonged electrolysis time. The test piece microcosmic iridium has better crystallization degree and higher density, provides electrolytic active sites, has more cracks and larger specific surface area.
According to the technical scheme, the titanium substrate is subjected to acid etching treatment, so that corresponding corrosion small holes are formed in the titanium substrate, and a catalyst coating is coated on the corroded titanium substrate, namely, the metallic elements iridium and tantalum are coated on the titanium substrate, and are uniformly distributed on the surface of the titanium substrate, so that a protective layer is well formed, the service life of the electrode is prolonged, the electrolytic voltage is reduced, the electrolytic copper foil anode is particularly suitable for an electrolytic copper foil anode, the service life of a related DSA anode is prolonged, lower electrolytic energy consumption is obtained, and the electrolytic efficiency is improved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application, and are intended to be included within the scope of the appended claims and description. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (9)
1. A method for preparing an anode for electrolysis, the method comprising:
selecting a titanium substrate as an anode substrate; the titanium substrate is of a net-shaped structure or a plate-shaped structure, and the thickness is 0.1-8 mm;
carrying out surface pretreatment on the titanium substrate, wherein the surface pretreatment at least comprises surface degreasing, sand blasting and shape correction;
acid etching is carried out on the titanium substrate; wherein the acid etching treatment comprises soaking for 1-2.5 hours by 5-18% hydrochloric acid, or boiling for 2-6 hours by 7-15% oxalic acid, or boiling for 1-4 hours by 10-20% sulfuric acid;
cleaning and drying the titanium substrate;
and (3) coating a catalyst coating on the titanium substrate after the drying treatment until the catalyst coating reaches a set coating amount.
2. The method of claim 1, wherein the catalyst coating is configured by:
iridium and tantalum are mixed according to the following proportion of (5-80): (5 to 50) in a molar ratio in an organic solvent or an inorganic solvent as a coating solution of the catalyst coated on the titanium substrate.
3. The method of claim 2, wherein the organic solvent comprises one or a mixture of two of n-butanol, isopropanol, and ethanol.
4. The method of claim 2, wherein the inorganic solvent comprises a hydrochloric acid solution.
5. A method according to claim 2, wherein iridium and tantalum are mixed according to (5-80): the molar ratio of (5-50) is mixed in an organic solvent or an inorganic solvent, comprising:
any one of iridium tetrachloride, iridium trichloride, chloroiridic acid, bromoiridic acid and iridium acetate is selected;
any one of tantalum chloride hydrochloric acid solution, n-butyl alcohol tantalum solution, ethanol tantalum and butanediol tantalum is selected;
the iridium solution and the tantalum solution are selected, so that the molar ratio of iridium to tantalum is (5-80): the section of (5) to (50), a catalyst coating layer is formed.
6. The method of claim 1, wherein said applying a catalyst coating to said titanium substrate after said drying treatment until said catalyst coating reaches a set application amount comprises:
uniformly brushing the catalyst coating solution on the titanium substrate after the drying treatment by a mechanical brushing mode and an electrostatic spraying mode, drying, then, implanting into a high-temperature furnace for burning at 440-5500 ℃, preserving heat for 10-90 minutes, and repeating the coating process after cooling until the catalyst coating reaches the preset coating amount.
7. The method of any one of claims 1 to 6, wherein the mesh substrate comprises a cell plate mesh, a woven mesh; the thickness of the mesh-shaped base material is preferably 0.3 to 2mm.
8. The method according to any one of claims 1 to 6, wherein the thickness of the plate-like substrate is preferably 1 to 7mm.
9. An anode for electrolysis, characterized in that the anode for electrolysis is prepared by the method for preparing an anode for electrolysis according to any one of claims 1 to 8.
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| CN202310218182.9A CN117026313A (en) | 2023-03-08 | 2023-03-08 | Method for producing anode for electrolysis and anode for electrolysis |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310218182.9A CN117026313A (en) | 2023-03-08 | 2023-03-08 | Method for producing anode for electrolysis and anode for electrolysis |
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