CN111926309A - Titanium-based passivation prevention coating for metal oxide electrode and preparation method thereof - Google Patents
Titanium-based passivation prevention coating for metal oxide electrode and preparation method thereof Download PDFInfo
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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Abstract
The invention discloses a titanium-based anti-passivation coating for a metal oxide electrode, which consists of a transition layer and a functional coating, wherein the transition layer is conductive TiO2The functional coating is SnO2The base composite coating comprises the following chemical components: SnO as titanium-based protective component2The modifier accounts for 100 percent of the total molar percentage, wherein the titanium-based protective component SnO2The molar fraction of the metal oxide is not less than 90 percent, the balance is modifier, the modifier is one of high-valence base metal oxide and noble metal oxide, the coating obtained by the invention has the characteristics of low cost, controllable deposition, uniform component, compact structure, high stability and environmental friendliness, and is easy to realizeThe method realizes the design of coating components, has simple process, is suitable for large-scale production, and solves the problems of high cost, difficult control of Sn deposition and poor stability in the prior art.
Description
The technical field is as follows:
the invention relates to a titanium-based anti-passivation coating for a metal oxide electrode and a preparation method thereof.
Background art:
the metal oxide electrode is an electrode formed by coating a valve-shaped substrate with a metal oxide, and has wide applications in the fields of electrolysis, electroplating, aluminum foil formation, cathodic protection, and the like. The metal oxide electrode usually uses pure titanium as the base material of the electrode. Studies have shown that the failure of metal oxide electrodes is due in part to passivation of the titanium substrate surface to form a non-conductive titanium oxide film. In order to delay the passivation of titanium base and prolong the service life of oxide electrode, a coating (plating) layer with good corrosion resistance, good conductivity and low electrochemical activity, such as a noble metal coating, is generally introduced between the titanium base and the active oxide coating. The current typical coating layers comprise Pt coating layer and SnO2-Sb2O3And (4) coating. Tao Zin et al (Tao Zin et al, the performance of platinum intermediate layer preparation on iridium tantalum coating titanium anode performance. materials science and engineering, 2004,22(2):240) reported that 3 processes such as electroplating, brush plating and magnetron sputtering were used to prepare Pt coating. Research results show that the Pt coating has good oxidation resistance, the iridium tantalum oxide anode containing the Pt coating has long service life, but the Pt is expensive and has high manufacturing cost, and the application of the electrode is limited. SnO2-Sb2O3The coating (Sonchi et al, research progress of titanium-based oxide anode intermediate layer, electrochemistry, 2013, 19(4):313) is generally prepared by an inorganic chloride thermal decomposition method, and the coating is low in price, corrosion resistant but difficult to control Sn deposition in the coating and poor in stability.
The invention content is as follows:
the invention aims to provide a titanium-based anti-passivation coating for a metal oxide electrode and a preparation method thereof, which have the characteristics of low cost, controllable deposition, high stability and environmental friendliness and solve the problems of high cost, difficult control of Sn deposition and poor stability in the prior art.
The invention is realized by the following technical scheme:
the titanium-based anti-passivation coating for the metal oxide electrode consists of a transition layer and a functional coating, wherein the transition layer is conductive TiO2Film layer, said functionThe coating is SnO2The base composite coating comprises the following chemical components: SnO as titanium-based protective component2The modifier accounts for 100 percent of the total molar percentage, wherein the titanium-based protective component SnO2The mole fraction of the modifier is not less than 90 percent, and the balance is the modifier which is one of high-valence base metal oxide and noble metal oxide.
The high valence base metal oxide is Ta2O5、Nb2O5。
The noble metal oxide is RuO2、IrO2。
The thickness of the functional coating is 0.5-5 mu m.
Tin dioxide SnO2Low cost and no obvious toxicity. Tin dioxide has good corrosion resistance in acid environment, enamel property and TiO2The film has high adhesion strength and can provide effective protection for the titanium base.
The modifier has low content, low additional cost and stability in acid environment, and has the functions of improving the conductivity of the oxide coating and improving the chemical stability of the coating.
The functional coating is less than 0.5 mu m, the titanium base cannot be effectively protected, and the bonding force with the titanium base is reduced when the thickness of the functional coating is more than 5 mu m, so that the ideal thickness of the coating is 0.5-5 mu m.
The preparation method of the passivation preventing coating comprises the following steps:
firstly, etching a titanium material for 2-4 hours at 85-95 ℃ by using 5-10% (mass fraction) oxalic acid solution, washing with water, and drying at room temperature;
secondly, pre-oxidizing the titanium base for 5-15 min at 400-450 ℃ in air atmosphere to obtain a transition layer;
uniformly coating the coating liquid on the transition layer; the coating liquid comprises the following components in percentage by mole based on 100 percent of total coating liquid metal: the molar fraction of the Sn organic precursor is not less than 90%, the rest is a modifier precursor, the solvents are ethanol and n-butyl alcohol, and the concentration of metal ions in the coating liquid is 0.1-0.4 mol/L; the coating liquid has high concentration and less coating times; the concentration is small, the coating times are many, and the coating is flexible to use in operation;
fourthly, curing for 10 to 15min at the temperature of 100 to 120 ℃;
performing thermal oxidation decomposition at 450-520 ℃ for 10-15 min;
sixthly, heat treatment is carried out for 1 hour at the temperature of 450-520 ℃.
The titanium base surface, which is usually placed in an atmospheric environment, is covered with a layer of loose titanium oxide, and the oxide film layer can affect the binding force of the titanium base and a subsequent coating. The oxalic acid is used for removing the titanium oxide film layer on the titanium base surface to obtain a clean base body.
The pre-oxidation is to prefabricate a conductive titanium oxide thin layer on the surface of the titanium base to form a transition layer, aiming at improving the titanium base and SnO2The bonding force between the base composite coatings. During pre-oxidation, the titanium-based surface keeps air flowing. And if the time exceeds 15min, an insulating film layer is easy to generate, and the pre-oxidation time is preferably 5-15 min.
The Sn organic precursor is alkoxy tin and tin acetate. Compared with tin chloride, the organic precursor has higher boiling point, less volatilization and higher tin deposition rate.
The modifier precursor is one of high-valence base metal and noble metal precursor; the high-valence base metal precursor is selected from one of tantalum chloride, tantalum penta-n-butoxide, fluoroniobate and niobium oxalate, preferably tantalum penta-n-butoxide and niobium oxalate.
The noble metal precursor is any one of ruthenium chloride, iridium trichloride and chloroiridic acid, preferably ruthenium chloride and chloroiridic acid.
The coating can be brush coating, dip coating and spray coating. When brushing is selected, the force is moderate, and the longitudinal brushing and the transverse brushing are alternately carried out to ensure the uniformity of the coating. When dip coating is adopted, the pulling speed is 1-50 mu m/s. When spraying is adopted, the air inlet pressure is 0.2-0.5 MPa, and the spraying distance is 20-30 cm. The spray pattern is preferred in view of ease of automation of the operation, uniformity and consistency of the coating.
The solidification is to remove the organic solvent under the action of heat and attach the precursor to the surface of the titanium-based transition layer. When the temperature is higher than 120 ℃, the solvent is volatilized too fast, the binding force of the coating is influenced, and the drying and curing are generally carried out at 100-120 ℃.
Thermal oxidative decomposition is the conversion of precursors to metal oxides. When the temperature is lower than 450 ℃, the oxidative decomposition of the metal precursor is incomplete. When the temperature is higher than 520 ℃, the titanium material can be seriously oxidized, so that the ideal thermal oxidation decomposition temperature is 450-520 ℃, and preferably 480-500 ℃.
The heat treatment is to eliminate the internal stress in the composite coating and improve the binding force among the titanium base, the transition layer and the functional coating. When the temperature is higher than 520 ℃, the titanium material can be seriously oxidized, so the ideal heat treatment temperature is 450-520 ℃.
The invention has the following beneficial effects:
the coating obtained by the invention has the characteristics of low cost, controllable deposition, uniform components, compact structure, high stability and environmental friendliness, is easy to realize the design of coating components, has simple process, is suitable for large-scale production, and solves the problems of high cost, difficult control of Sn deposition and poor stability in the prior art.
Description of the drawings:
FIGS. 1 to 4 are scanning electron micrographs of the anti-passivation coatings prepared in examples 1 to 4, respectively.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
a pure titanium sheet TA2 is selected as a matrix, 10 percent (mass fraction) of oxalic acid is used for etching for 3 hours at 90 ℃, the substrate is washed by water and dried at room temperature, and then pre-oxidized for 10 minutes at 400 ℃ to obtain a titanium oxide transition layer. According to the molar ratio of tin to tantalum metal of 9: dissolving tin alkoxide and tantalum pentachloride in a volume ratio of 1: 1, obtaining a coating liquid with the total metal molar concentration of 0.20 mol/L. The titanium oxide transition layer is uniformly coated with a soft brush each time, then dried and cured at 110 ℃ for 10min, and then thermally oxidized and decomposed at 480 ℃ for 10min, and the steps are repeated until the coating liquid is completely coated. Finally, heat treatment is carried out for 1h at 500 ℃ to prepare Ti/TiO2/SnO2-Ta2O5And (4) coating.
Scanning electron microscope tests show that the anti-passivation coating is compact in structure and small and few in cracks as shown in figure 1. The energy spectrum analysis showed that the tin deposition rate was 99%.
Comparative example 1:
referring to example 1, the difference is that 5-10% (mass fraction) oxalic acid solution is used for etching titanium material at 85-95 ℃ for 2-4 h, titanium oxide transition layer is obtained after washing and drying at room temperature without pre-oxidation, and coating liquid is directly coated on clean titanium base to obtain Ti/SnO2-Ta2O5And (4) coating.
Comparative example 2:
referring to example 1, the difference is that 5-10% (mass fraction) oxalic acid solution is used for etching titanium material at 85-95 ℃ for 2-4 h, titanium oxide transition layer is obtained without pre-oxidation after washing and drying at room temperature, coating liquid is directly coated on clean titanium base, and antimony trichloride is used for replacing tantalum pentachloride to obtain Ti/SnO2-Sb2O3And (4) coating.
For ease of comparison, the Ti/SnO obtained in comparative example 1 was tested in a 0.5mol/L sulfuric acid solution2-Ta2O5Coating, Ti/SnO obtained in comparative example 22-Sb2O3Coating, example 1 Ti/TiO2/SnO2-Ta2O5Open circuit potential of the coating. The test results were as follows: Ti/SnO obtained in comparative example 12-Ta2O5The open-circuit potential of the coating is 0.42V, and Ti/SnO2-Sb2O3The open circuit potential of the coating is 0.36V (VsSCE), Ti/TiO2/SnO2-Ta2O5The open circuit potential of the coating was 0.55V. Thus, example 1 gave Ti/TiO2/SnO2-Ta2O5The chemical stability of the coating is high.
Respectively using a round shaft with the diameter of 12mm to separate Ti/SnO2-Ta2O5Coating sample and Ti/TiO2/SnO2-Ta2O5The coated samples were bent to be parallel and a small amount of peeling off was found at the former bend. Therefore, the titanium base and SnO of the titanium base and the titanium oxide thin layer prepared on the titanium base surface by pre-oxidation in the embodiment 1 are improved compared with the titanium base and SnO prepared in the comparative example 12Base compositeThe bonding force between the coatings.
Example 2
Pure titanium mesh TA2 is selected as a matrix, 8 percent (mass fraction) of oxalic acid is used for etching at 85 ℃ for 4 hours, the pure titanium mesh is washed by water and dried at room temperature, and then pre-oxidized at 450 ℃ for 12min to obtain a titanium oxide transition layer. According to the molar ratio of tin to niobium metal of 9.5: 0.5, dissolving tin acetate and niobium oxalate in a volume ratio of 1: 1, obtaining a coating liquid with the total metal molar concentration of 0.25 mol/L. Immersing the titanium base with the titanium oxide transition layer in the coating liquid, pulling at the speed of 20 μm/s, standing at room temperature for 5min, drying and curing at 120 deg.C for 12min, and performing thermal oxidative decomposition at 500 deg.C for 10min, repeating for 5 times. Finally, heat treatment is carried out for 1h at 500 ℃ to prepare Ti/TiO2/SnO2-Nb2O5And (4) coating.
Scanning electron microscope tests show that the anti-passivation coating is compact in structure and small and few in cracks as shown in figure 2.
Example 3
A pure titanium sheet TA2 is selected as a matrix, 10 percent (mass fraction) of oxalic acid is used for etching for 3 hours at 90 ℃, the substrate is washed by water and dried at room temperature, and then pre-oxidized for 10 minutes at 420 ℃ to obtain a titanium oxide transition layer. According to the molar ratio of tin to ruthenium metal of 9: dissolving tin alkoxide and ruthenium chloride in a volume ratio of 1: 1, obtaining a coating liquid with the total metal molar concentration of 0.30 mol/L. The titanium oxide transition layer is uniformly coated with a soft brush each time, then dried and cured at 110 ℃ for 10min, and then thermally oxidized and decomposed at 450 ℃ for 10min, and the steps are repeated until the coating liquid is completely coated. Finally, heat treatment is carried out for 1h at 480 ℃ to prepare Ti/TiO2/SnO2-RuO2And (4) coating.
Scanning electron microscope tests show that the anti-passivation coating is compact in structure and small and few in cracks as shown in figure 3. Open circuit potential OCP test results in 0.5mol/L sulfuric acid solution: Ti/TiO 22/SnO2-RuO2It was 0.65V.
Example 4
Selecting a pure titanium sheet TA2 as a matrix, etching for 3h by using 10 percent (mass fraction) of oxalic acid at 95 ℃, washing, drying at room temperature, pre-oxidizing for 15min at 450 ℃,and obtaining the titanium oxide transition layer. According to the molar ratio of tin to iridium metal of 9.2: 0.8, dissolving alkoxy tin and chloroiridic acid in a volume ratio of 1: 1, obtaining a coating liquid with the total metal molar concentration of 0.20 mol/L. When spraying, the air inlet pressure is 0.4MPa, and the spraying distance is 25 cm. Then drying and curing at 110 ℃ for 10min, and then thermal oxidative decomposition at 480 ℃ for 15min, and repeating until the thickness of the composite coating is 5 μm. Finally, heat treatment is carried out for 1h at 480 ℃ to prepare Ti/TiO2/SnO2-IrO2And (4) coating.
Scanning electron microscope tests show that the anti-passivation coating has few and small cracks and a compact structure as shown in FIG. 4. Open circuit potential OCP test results in 0.5mol/L sulfuric acid solution: Ti/TiO 22/SnO2-IrO2The coating was 0.55V.
Claims (10)
1. The titanium-based passivation preventing coating for the metal oxide electrode is characterized by comprising a transition layer and a functional coating, wherein the transition layer is conductive TiO2The functional coating is SnO2The base composite coating comprises the following chemical components: SnO as titanium-based protective component2The modifier accounts for 100 percent of the total molar percentage, wherein the titanium-based protective component SnO2The mole fraction of the modifier is not less than 90 percent, and the balance is the modifier which is one of high-valence base metal oxide and noble metal oxide.
2. The titanium-based passivation preventing coating for a metal oxide electrode according to claim 1, wherein the high valence base metal oxide is Ta2O5、Nb2O5Any one of the above.
3. The titanium-based passivation preventing coating for metal oxide electrode according to claim 1, wherein said noble metal oxide is RuO2、IrO2。
4. The titanium-based passivation preventing coating for a metal oxide electrode according to claim 1, wherein the thickness of the functional coating is 0.5 to 5 μm.
5. The method for preparing a titanium-based passivation preventing coating for a metal oxide electrode according to claim 1, comprising the steps of:
firstly, etching a titanium material for 2-4 hours at 85-95 ℃ by using 5-10% (mass fraction) oxalic acid solution, washing with water, and drying at room temperature;
secondly, pre-oxidizing the titanium base obtained in the step one at 400-450 ℃ for 5-15 min in an air atmosphere to obtain a transition layer;
uniformly coating the coating liquid on the transition layer; the coating liquid comprises the following components in percentage by mole based on 100 percent of total coating liquid metal: the molar fraction of the Sn organic precursor is not less than 90%, the rest is a modifier precursor, the solvents are ethanol and n-butyl alcohol, and the concentration of metal ions in the coating liquid is 0.1-0.4 mol/L;
fourthly, curing for 10 to 15min at the temperature of 100 to 120 ℃;
performing thermal oxidation decomposition at 450-520 ℃ for 10-15 min;
sixthly, heat treatment is carried out for 1 hour at the temperature of 450-520 ℃.
6. The method for preparing the titanium-based passivation preventing coating for the metal oxide electrode according to claim 5, wherein the Sn organic precursor is one of alkoxy tin and tin acetate; the modifier precursor is one of high-valence base metal and noble metal precursor.
7. The method for producing a titanium-based passivation preventing coating for a metal oxide electrode according to claim 6, wherein the high-valence base metal precursor is any one selected from tantalum chloride, tantalum penta-n-butoxide, fluoroniobic acid, and niobium oxalate.
8. The method of preparing a titanium-based passivation preventing coating for a metal oxide electrode according to claim 6, wherein the noble metal precursor is any one of ruthenium chloride, iridium trichloride, and chloroiridic acid.
9. The method for producing a titanium-based passivation preventing coating for a metal oxide electrode according to claim 5, wherein the coating is performed by any one of brush coating, dip coating and spray coating; when brushing is selected, longitudinal brushing and transverse brushing are alternately carried out; when dip coating is adopted, the pulling speed is 1-50 mu m/s; when spraying is adopted, the air inlet pressure is 0.2-0.5 MPa, and the spraying distance is 20-30 cm.
10. The method for preparing a titanium-based passivation preventing coating for a metal oxide electrode according to claim 5, wherein a thermal oxidation decomposition temperature is 480 to 500 ℃.
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| WO2023088398A1 (en) * | 2021-11-22 | 2023-05-25 | 广东省科学院资源利用与稀土开发研究所 | Composite oxide coating electrode for organic pollutant degradation, and preparation method therefor |
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| CN113363419B (en) * | 2021-06-23 | 2023-01-20 | 天津市捷威动力工业有限公司 | Negative pole piece and preparation method and application thereof |
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| WO2023088398A1 (en) * | 2021-11-22 | 2023-05-25 | 广东省科学院资源利用与稀土开发研究所 | Composite oxide coating electrode for organic pollutant degradation, and preparation method therefor |
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