CN109402632B - Electrode coating solution precursor, electrode coating solution, coated electrode and preparation method thereof - Google Patents
Electrode coating solution precursor, electrode coating solution, coated electrode and preparation method thereof Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 138
- 238000000576 coating method Methods 0.000 title claims abstract description 138
- 239000002243 precursor Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 112
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 26
- 229940061720 alpha hydroxy acid Drugs 0.000 claims abstract description 20
- 150000001280 alpha hydroxy acids Chemical class 0.000 claims abstract description 20
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 18
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 31
- 239000010936 titanium Substances 0.000 claims description 31
- 229910052719 titanium Inorganic materials 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000001630 malic acid Substances 0.000 claims description 6
- 235000011090 malic acid Nutrition 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 238000005054 agglomeration Methods 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- -1 titanium hydride Chemical compound 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to an electrode coating solution precursor, an electrode coating solution, a coated electrode and a preparation method thereof, belonging to the technical field of electrochemistry, wherein the electrode coating solution precursor is prepared by mixing chloroiridic acid, stannic chloride, α -hydroxy acid and acetic acid solution and evaporating to dryness at the temperature of 145-150 ℃, and the electrode coating solution is prepared by dissolving the electrode coating solution precursor and tantalum pentachloride into an organic mixed solution together.
Description
Technical Field
The invention relates to the technical field of electrochemistry, and in particular relates to an electrode coating solution precursor, an electrode coating solution, a coated electrode and a preparation method thereof.
Background
In the prior art, the preparation process of the coating electrode usually causes uneven distribution of the surface coating of the titanium electrode, loose structure and a large number of cracks on the surface of the coating. When the coated titanium electrode is used, gas separated out from the anode erodes to the surface of the titanium substrate through cracks, so that the surface of the titanium substrate is oxidized and fails, and the electrochemical catalytic performance and the service life of the coated titanium electrode are seriously influenced.
Disclosure of Invention
The invention aims to provide an electrode coating solution precursor, which can uniformly disperse crystalline substances in an electrode coating solution and avoid agglomeration.
The second purpose of the invention is to provide an electrode coating solution, which can effectively avoid uneven distribution and loose structure of a surface coating of a titanium electrode and a large number of cracks on the surface of the coating caused by agglomeration of metal crystal particles in the process of preparing a coated electrode.
The third purpose of the invention is to provide a preparation method of the coating electrode, which is simple, easy to operate and suitable for industrial production.
The fourth purpose of the invention is to provide a coated electrode prepared by the preparation method, which has higher electrocatalytic activity and longer service life.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the invention provides an electrode coating solution precursor, which is prepared by mixing chloroiridic acid, stannic chloride, α -hydroxy acid and acetic acid solution and evaporating at the temperature of 145-150 ℃.
The invention also provides an electrode coating solution, which is prepared by dissolving the electrode coating solution precursor and tantalum pentachloride in an organic mixed solution together.
The invention also provides a preparation method of the coating electrode, which comprises the following steps: coating the electrode coating solution on the surface of the titanium plate, drying at the temperature of 142-150 ℃, carrying out hot air oxidation for 10-20min at the temperature of 480-510 ℃, cooling, repeating the coating, drying, hot air oxidation and cooling processes for 14-20 times, and then carrying out heat treatment for 1-1.5h at the temperature of 480-510 ℃.
The invention also provides the coated electrode prepared by the preparation method.
The electrode coating solution precursor, the electrode coating solution, the coated electrode and the preparation method thereof provided by the preferred embodiment of the application have the beneficial effects that:
the precursor of the electrode coating solution can enable crystalline substances in the electrode coating solution to be uniformly dispersed, and agglomeration is avoided. The electrode coating solution further obtained from the electrode coating solution precursor can effectively avoid uneven distribution and loose structure of the surface coating of the titanium electrode and a large number of cracks on the surface of the coating caused by agglomeration of metal crystal particles in the process of preparing the coated electrode. In addition, the application also provides a preparation method of the coated electrode, and the method is simple, easy to operate and capable of realizing industrial production. The coating electrode prepared by the preparation method has higher electrocatalytic activity and longer service life.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an SEM scanning electron micrograph of a coated electrode obtained in example 13 of Experimental example 1 of the present application;
FIG. 2 is an SEM scanning electron micrograph of a coated electrode obtained in example 14 of Experimental example 1 of the present application;
FIG. 3 is an SEM scanning electron micrograph of a coated electrode obtained in comparative example 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The electrode coating solution precursor, the electrode coating solution, the coated electrode and the method for preparing the same of the present application will be specifically described below.
The precursor of the electrode coating solution provided by the application is to treat the crystalline raw material used in the electrode coating solution to be prepared. The inventor finds that the operation can effectively improve the dispersion degree of crystal particles in the electrode coating solution, obviously reduce the agglomeration degree of metal crystal particles compared with the electrode coating solution prepared by directly preparing raw materials, and improve the electrochemical catalytic performance and the service life of the coating electrode.
In some embodiments, the electrode coating solution precursor can be obtained by mixing chloroiridic acid, stannic chloride and α -hydroxy acid with acetic acid solution, and evaporating at 145-150 ℃ to dryness, wherein chloroiridic acid is mainly used for providing conductivity and catalytic active components, and stannic chloride is mainly used for reinforcing the catalytic active components.
The inventor finds that α -hydroxy acid can obviously improve the performance of dispersing and suspending metal crystal particles under the action of acetic acid, so that the metal crystal particles can be fully diffused under the mutual matching action of α -hydroxy acid and acetic acid, and the rapid growth and agglomeration of the metal crystal particles can be fully inhibited in the subsequent processes of evaporation to dryness, thermal oxidation and the like.
It is worth noting that the acetic acid solution can be replaced by other similar acidic organic reagents, but the acetic acid solution can be matched with α -hydroxy acid to enable the chloroiridic acid and the stannic chloride to have better dispersion and suspension properties compared with other acidic organic reagents.
In the present application, after mixing chloroiridic acid, stannic chloride, α -hydroxy acid and acetic acid solution, the mixture is evaporated to dryness at 145-150 ℃, alternatively, the evaporation temperature may be, for example, 145 ℃, 146 ℃, 147 ℃, 148 ℃, 149 ℃ or 150 ℃, may be 145.5 ℃, 146.5 ℃, 147.5 ℃, 148.5 ℃ or 149.5 ℃, and may be any temperature value within the range of 145-150 ℃.
If the evaporation temperature is higher than 150 ℃, the evaporation speed is too high, the metal crystal particles are not diffused sufficiently, so that the crystalline substance cannot be dispersed uniformly, and if the evaporation temperature is lower than 145 ℃, the dissolution and diffusion speed of α -hydroxy acid are too low, so that the diffusion uniformity of the metal crystal particles is reduced.
In some embodiments, the mass ratio of the chloroiridic acid, the stannic chloride and the α -hydroxy acid may be 63-65: 2-4: 8-10 in sequence, that is, the chloroiridic acid, the stannic chloride and the α -hydroxy acid may be freely combined in the range of 63-65 (such as 63, 63.5, 64, 64.5 or 65) and 2-4 (such as 2, 2.5 or 3) and 8-10 (such as 8, 8.5, 9, 9.5 or 10) respectively.
Alternatively, the α -hydroxy acid may include, but is not limited to, at least one of citric acid, tartaric acid, malic acid, and lactic acid, for example.
Bearing, the electrode coating solution precursor that this application provided can make the crystalline state substance dispersion in the electrode coating solution even, effectively avoids the reunion.
Further, the application also provides an electrode coating solution, and the electrode coating solution can be prepared by dissolving the electrode coating solution precursor and tantalum pentachloride in an organic mixed solution. Among them, tantalum pentachloride is mainly used to provide non-conductive oxide component, so as to make the conductive oxide structure more stable.
In some embodiments, the mass ratio of tantalum pentachloride to chloroiridic acid may be 30 to 33: 63-65, i.e., the tantalum pentachloride and the chloroiridic acid can be freely combined in the range of 30-33 (such as 30, 30.5, 31, 31.5, 32, 32.5 or 33, etc.) and 63-65 (such as 63, 63.5, 64, 64.5 or 65, etc.), respectively.
In one embodiment, the mass ratio of the chloroiridic acid to the stannic chloride to the α -hydroxy acid to the tantalum pentachloride is 64:3: 9: 32 in sequence, and under the mixture ratio, the metal crystal particles in the electrode coating solution have the best dispersion and diffusion effects and basically have no agglomeration phenomenon.
In some embodiments, the organic mixed solution contains both ethylene glycol and n-butanol. In some preferred embodiments, the organic mixed solution may contain ethylene glycol and n-butanol in a volume ratio of 0.8 to 1: 0.85-1.15, that is, the ethylene glycol and the n-butanol can be freely combined in the range of 0.8-1 (such as 0.8, 0.85, 0.9, 0.95 or 1) and 0.85-1.15 (such as 0.85, 0.9, 0.95, 1, 1.05, 1.1 or 1.15) respectively.
The ethylene glycol and the n-butanol in the proportion range are used as the organic mixed solution, so that the diffusivity of the solvent and the uniformity of the coating solution can be enhanced.
In the present application, the concentration of chloroiridic acid in the electrode coating solution may be 39 to 42 g/L, for example, 39 g/L, 40 g/L, 41 g/L, 42 g/L, etc., may be 39.5 g/L, 40.5 g/L, 41.5 g/L, etc., and may be any concentration value within the range of 39 to 42 g/L.
In conclusion, the electrode coating solution further obtained from the electrode coating solution precursor provided by the application can effectively avoid uneven distribution and loose structure of the surface coating of the titanium electrode caused by agglomeration of metal crystal particles and a large amount of cracks on the surface of the coating in the process of preparing the coating electrode.
In addition, the application also provides a preparation method of the coating electrode, which can comprise the following steps: coating the electrode coating solution on the surface of the titanium plate, drying at the temperature of 142-150 ℃, carrying out hot air oxidation for 10-20min at the temperature of 480-510 ℃, cooling, repeating the coating, drying, hot air oxidation and cooling processes for 14-20 times, and then carrying out heat treatment for 1-1.5h at the temperature of 480-510 ℃.
Before the electrode coating solution is applied, the titanium plate is subjected to a treatment comprising: soaking the titanium plate in 5-8wt% sulfamic acid solution for 20-30min, and then cleaning and drying; boiling in 6.5-8wt% oxalic acid solution for 75-80min, washing, and oven drying.
Wherein, the titanium substrate is soaked in sulfamic acid solution with the concentration, which is mainly used for removing oil stains stained in the processing process of the titanium substrate. It is worth explaining that the degreasing process of the method is carried out at normal temperature, and no heating process is needed in the degreasing process, so that on one hand, the method is beneficial to saving energy, and on the other hand, the bonding force between a titanium substrate and an electrode coating solution can be improved.
The subsequent boiling in oxalic acid solution is mainly to form dark gray titanium hydride on the surface of the titanium substrate, and it is worth explaining that if the oxalic acid concentration is too high or the boiling time is too long, the consumption of oxalic acid is wasted, and the generated titanium oxalate is too high in concentration and precipitated on the titanium substrate, so that the acid etching effect is influenced.
The hot air oxidation is carried out for 10-20min at the temperature of 480-510 ℃, so that the chloride in the coating can be completely oxidized. When the temperature is lower than 480 ℃, the chlorine content in the coating is higher; above 510 c, the oxygen content in the coating decreases instead, probably due to the coatingThe oxide in the layer being composed of non-stoichiometric oxides, e.g. IrO2-XAnd TiO2-XThe coating belongs to oxygen-deficient oxide, and the structure of the oxide in the coating is changed at the moment, so that the surface appearance of the coating is changed.
In the application, the titanium substrate surface coating is formed by multiple times of brushing, the first layer of the surface coating is relatively porous, and oxygen in the thermal oxidation process can penetrate through the porous first layer when the coating is brushed to react with the metal chloride of the lower layer to generate metal oxide, so that the porosity of the coating is reduced along with the increase of the brushing times. After 14-20 times of brushing, the coating reaches a compact degree, and the manufacturing cost of the electrode is increased by more than 20 times.
The prepared coating electrode has the advantages that the surface of the coating has no obvious cracks, the area of a plane area is large and smooth, most of crystal grains grow in the plane area, and the coating is combined compactly; and the coated electrode has higher electrocatalytic activity and longer service life.
In some embodiments, the coated electrode has a grain average particle size of 7 to 11 nm. In some embodiments, the grains of the coated electrode have an average grain size of no more than 8nm, which makes the planar area of the coating surface larger and the cracks finer than if the average grain size exceeded 8 nm.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides an electrode coating solution precursor, which is prepared by adding chloroiridic acid, tin tetrachloride and malic acid into an acetic acid solution in a mass ratio of 63:2:8, and then evaporating to dryness at 145 ℃.
Example 2
The embodiment provides an electrode coating solution precursor, which is prepared by adding chloroiridic acid, tin tetrachloride and malic acid into an acetic acid solution in a mass ratio of 65:4:10, and then evaporating to dryness at 145 ℃.
Example 3
The embodiment provides an electrode coating solution precursor, which is prepared by adding chloroiridic acid, tin tetrachloride and malic acid into an acetic acid solution in a mass ratio of 64:3:9, and then evaporating to dryness at 145 ℃.
Example 4
This example differs from example 1 in that the α -hydroxy acid is citric acid.
Example 5
This example differs from example 1 in that the α -hydroxy acid is tartaric acid.
Example 6
This example differs from example 1 in that the α -hydroxy acid is lactic acid.
Example 7
The difference between the embodiment and the embodiment 1 is that α -hydroxy acid is prepared by mixing malic acid and citric acid in a mass ratio of 1:1.
Example 8
This example differs from example 1 in that: the evaporation to dryness is carried out at 148 ℃.
Example 9
This example differs from example 1 in that: the evaporation to dryness is carried out at 150 ℃.
Example 10
The embodiment provides an electrode coating solution, which is prepared by dissolving an electrode coating solution precursor and tantalum pentachloride into an organic mixed solution together, wherein the concentration of chloroiridic acid in the electrode coating solution is 39 g/L.
The electrode coating solution precursor is provided in embodiment 1, the mass ratio of tantalum pentachloride to chloroiridic acid in the electrode coating solution precursor raw material is 30:63, and the organic mixed solution is obtained by mixing ethylene glycol and n-butanol at a volume ratio of 1:1.
Example 11
The embodiment provides an electrode coating solution, which is prepared by dissolving an electrode coating solution precursor and tantalum pentachloride into an organic mixed solution together, wherein the concentration of chloroiridic acid in the electrode coating solution is 40 g/L.
The electrode coating solution precursor is provided in embodiment 2, the mass ratio of tantalum pentachloride to chloroiridic acid in the electrode coating solution precursor raw material is 33:65, and the organic mixed solution is obtained by mixing ethylene glycol and n-butanol at a volume ratio of 0.8: 0.85.
Example 12
The embodiment provides an electrode coating solution, which is prepared by dissolving an electrode coating solution precursor and tantalum pentachloride into an organic mixed solution together, wherein the concentration of chloroiridic acid in the electrode coating solution is 42 g/L.
The electrode coating solution precursor is provided in embodiment 3, the mass ratio of tantalum pentachloride to chloroiridic acid in the electrode coating solution precursor raw material is 32:64, and the organic mixed solution is obtained by mixing ethylene glycol and n-butanol in a volume ratio of 1: 1.15.
Example 13
The embodiment provides a coated electrode, and the preparation method comprises the following steps:
soaking the titanium plate in 8wt% sulfamic acid solution for 30min, and then cleaning and drying; boiling in 6.5 wt% oxalic acid solution for 80min, washing, and oven drying.
The surface of the titanium plate was coated with the electrode coating solution provided in example 12, then dried at 142 ℃, then hot-air oxidized at 500 ℃ for 10min, cooled, and the coating, drying, hot-air oxidation and cooling processes were repeated 16 times, followed by heat treatment at 500 ℃ for 1 h.
Example 14
The embodiment provides a coated electrode, and the preparation method comprises the following steps:
soaking the titanium plate in sulfamic acid solution with the concentration of 7 wt% for 20min, and then cleaning and drying; boiling in 8wt% oxalic acid solution for 75min, cleaning, and oven drying.
The surface of the titanium plate was coated with the electrode coating solution provided in example 12, then dried at 150 ℃, then hot-air oxidized at 490 ℃ for 20min, cooled, and the coating, drying, hot-air oxidation and cooling processes were repeated 18 times, followed by heat treatment at 490 ℃ for 1.5 h.
Example 15
The embodiment provides a coated electrode, and the preparation method comprises the following steps:
soaking the titanium plate in 5 wt% sulfamic acid solution for 25min, and then cleaning and drying; boiling in 7 wt% oxalic acid solution for 78min, cleaning, and oven drying.
The surface of the titanium plate was coated with the electrode coating solution provided in example 11, then dried at 142 ℃, then hot-air oxidized at 480 ℃ for 15min, cooled, and the coating, drying, hot-air oxidation and cooling processes were repeated 14 times, followed by heat treatment at 480 ℃ for 1.2 h.
Example 16
The embodiment provides a coated electrode, and the preparation method comprises the following steps:
soaking the titanium plate in 7.5 wt% sulfamic acid solution for 25min, and then cleaning and drying; boiling in 7.5 wt% oxalic acid solution for 78min, cleaning, and oven drying.
The surface of the titanium plate was coated with the electrode coating solution of example 10, then dried at 145 deg.C, then hot-air oxidized at 510 deg.C for 15min, cooled, and the coating, drying, hot-air oxidation and cooling processes were repeated 20 times, followed by heat treatment at 510 deg.C for 1.5 h.
Test example 1
Taking the coated electrodes obtained in examples 13 and 14 as examples, a control group 1 is provided, and the difference between the control group 1 and 13 is that the former coated electrode is prepared by directly dissolving chloroiridic acid, stannic chloride, α -hydroxy acid and tantalum pentachloride in an organic mixed solution of ethylene glycol and n-butanol without preparing a coating solution precursor, and SEM scanning is performed on the coated electrode obtained in the above 3 groups of schemes, and scanning electron micrographs are shown in fig. 1 to 3.
As can be seen from FIG. 1, the coated electrode obtained in example 13 has no obvious cracks and relatively uniform grain distribution; as can be seen from FIG. 2, the coated electrode obtained in example 14 has no obvious cracks, fine crystal particles and relatively uniform grain distribution in the inner layer and the outer layer of the coating; as can be seen from fig. 3, the coated electrode obtained in the control 1 had significant cracks.
Test example 2
Using the coated electrodes obtained in example 13, example 14 and comparative example 1 of test example 1 as examples, comparative example 2 was set, and comparative example 2 was different from example 13 in that tin tetrachloride was not contained in the coating solution of comparative example 2, and the particle diameter of the surface of the coated electrode was measured by XRD, at a temperature of 40 ℃ and 0.5 mol/L H2SO4In aqueous solution, 500A/m2Measuring the oxygen evolution potential of the coating electrode; at 20000A/m2The enhanced life (time taken for the bath voltage to rise to 10V) of the coated electrode was measured, and the results are shown in Table 1.
TABLE 1 test results
The oxygen evolution potential of the iridium tantalum coating titanium coating electrode commonly used in the prior art is 1.39-1.44V, and the strengthening life is 1480-1550 hours by adopting the same test method, so that the coating electrode prepared by the embodiment of the application has obviously lower oxygen evolution potential and obviously longer strengthening life compared with the coating electrode of the same type in the prior art, and the technical scheme provided by the application can effectively improve the electrocatalytic activity of the coating electrode and prolong the service life of the coating electrode.
It can be seen from the comparison between example 1 and control group 1 that the coating solution prepared by preparing the coating solution precursor can obviously refine the average size of the crystal grains of the coated electrode, reduce the oxygen evolution potential of the electrode, and prolong the service life of the electrode, compared with the coating solution prepared by directly mixing the raw materials at one time without preparing the coating solution precursor.
It can be seen from the comparison of example 1 and control 2 that the raw material of the coating solution containing tin tetrachloride can significantly reduce the oxygen evolution potential of the electrode and prolong the service life of the electrode, compared with the raw material without tin tetrachloride.
To sum up, the precursor of the electrode coating solution provided by the application can enable crystalline substances in the electrode coating solution to be uniformly dispersed, and avoid agglomeration. The electrode coating solution further obtained from the electrode coating solution precursor can effectively avoid uneven distribution and loose structure of the surface coating of the titanium electrode and a large number of cracks on the surface of the coating caused by agglomeration of metal crystal particles in the process of preparing the coated electrode. In addition, the application also provides a preparation method of the coated electrode, and the method is simple, easy to operate and capable of realizing industrial production. The coating electrode prepared by the preparation method has higher electrocatalytic activity and longer service life.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (9)
1. An electrode coating solution is characterized in that the electrode coating solution is prepared by dissolving an electrode coating solution precursor and tantalum pentachloride in an organic mixed solution together;
mixing the precursor of the electrode coating solution with a solution of chloroiridic acid, stannic chloride, α -hydroxy acid and acetic acid, and evaporating to dryness at the temperature of 145-150 ℃;
the mass ratio of the chloroiridic acid to the stannic chloride to the α -hydroxy acid to the tantalum pentachloride is 64:3: 9: 32 in sequence.
2. The electrode coating solution of claim 1, wherein the α -hydroxy acid comprises at least one of citric acid, tartaric acid, malic acid, and lactic acid.
3. The electrode coating solution according to any one of claims 1 to 2, wherein the organic mixed solution contains both ethylene glycol and n-butanol.
4. The electrode coating solution according to claim 3, wherein the organic mixed solution contains the ethylene glycol and the n-butanol at a volume ratio of 0.8 to 1: 0.85-1.15.
5. The electrode coating solution of any one of claims 1-2, wherein the concentration of chloroiridic acid in the electrode coating solution is 39-42 g/L.
6. A preparation method of a coated electrode is characterized by comprising the following steps: coating the electrode coating solution as defined in any one of claims 1 to 5 on the surface of a titanium plate, drying at 142-150 ℃, hot air oxidizing at 480-510 ℃ for 10-20min, cooling, repeating the coating, drying, hot air oxidizing and cooling processes 14-20 times, and then heat treating at 480-510 ℃ for 1-1.5 h.
7. The production method according to claim 6, wherein the titanium plate is subjected to a treatment comprising: soaking the titanium plate in 5-8wt% sulfamic acid solution for 20-30min, and then cleaning and drying; boiling in 6.5-8wt% oxalic acid solution for 75-80min, washing, and oven drying.
8. A coated electrode produced by the production method according to claim 6 or 7.
9. The coated electrode of claim 8, wherein the coated electrode has a grain mean diameter of 7-11 nm.
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Application publication date: 20190301 Assignee: Guangzhou shunyao Energy Technology Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2024980006118 Denomination of invention: A precursor for electrode coating solution, electrode coating solution, coated electrode and its preparation method Granted publication date: 20200714 License type: Common License Record date: 20240523 Application publication date: 20190301 Assignee: Guangzhou Zhuoyue Power Technology Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2024980006061 Denomination of invention: A precursor for electrode coating solution, electrode coating solution, coated electrode and its preparation method Granted publication date: 20200714 License type: Common License Record date: 20240522 Application publication date: 20190301 Assignee: GUANGZHOU ZHUOYUE POWER NEW ENERGY Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2024980006026 Denomination of invention: A precursor for electrode coating solution, electrode coating solution, coated electrode and its preparation method Granted publication date: 20200714 License type: Common License Record date: 20240522 |