CN110387558B - Ruthenium-tantalum chlorine evolution electrode and preparation method and test method thereof - Google Patents
Ruthenium-tantalum chlorine evolution electrode and preparation method and test method thereof Download PDFInfo
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- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
Abstract
The invention relates to the field of chlor-alkali industry, in particular to a ruthenium-tantalum chlorine evolution electrode and a preparation method and a test method thereof. The ruthenium-tantalum chlorine evolution electrode substrate is titanium, and a ruthenium-tantalum mixture covers the surface of the substrate; the ruthenium-tantalum mixture is ruthenium oxide and tantalum oxide; and a TNTs intermediate layer is grown between the substrate and the RuTa mixture. The ruthenium-tantalum chlorine evolution electrode has good stability, catalytic activity and service life, and particularly shows obvious improvement on the aspect of service life; the preparation method is simple and efficient; the testing method can predict the service life of the electrode more accurately.
Description
Technical Field
The invention relates to the field of chlor-alkali industry, in particular to a ruthenium-tantalum chlorine evolution electrode and a preparation method and a test method thereof.
Background
The chlor-alkali industry is an important component of national economy, is the basic chemical raw material industry, and the industries of alkali, chlorine, chemical industry, metallurgy, papermaking, textile, petroleum and the like occupy very important basic positions when products such as industrial acid and the like are widely applied to building material systems in the whole country. In the chlor-alkali industry, salt is used as a raw material, industrial brine is electrolyzed to prepare caustic soda, hydrochloric acid, chlorine and hydrogen, and the chlorine is further prepared into various chlorine consumption products represented by polyvinyl chloride, at present, more than 200 chlorine consumption products can be produced in China, and the number of main varieties is more than 70. The chlor-alkali industry consumes 10% of the generated energy, so the high-efficiency gas electrode has great significance for energy conservation.
The metal oxide electrode has outstanding catalytic activity for chlorine evolution reaction, high stability and corrosion resistance in a chloride medium, and is mainly applied to industrial production related to a chlorine evolution electrode process. Currently, the most widely used DSA (Dimension stable anode) in chlor-alkali industry is the coating of RuO on titanium plate2Content (wt.)>The 30 at.% composite metal oxide has the advantages of good electrocatalytic activity, low overpotential, long service life and the like in oxygen evolution and chlorine evolution reactions, and is widely applied to a plurality of electrochemical fields, such as chlor-alkali production, metal plating, electrochemical plating, etc. in the chlor-alkali industry,Organic wastewater treatment, cathode protection and the like. Metal-coated anodes of this type are generally prepared by applying a mixture of noble metal oxides and tantalum pentoxide to a Ti support, in which RuO2And IrO2The ruthenium tantalum anode is the most widely used noble metal oxide, is also the preferred material of the oxygen evolution and chlorine evolution anode, has high chlorine evolution reactivity, long service life and stable performance as described above, and although the ruthenium tantalum anode has excellent performance as a chlorine evolution electrode in the chlor-alkali industry, the ruthenium tantalum anode still has some places to be improved, and the main problems are the dissolution and passivation of a Ti substrate and the formation of a non-conductive layer. This is because the ruthenium-tantalum anode coating prepared by the conventional thermal decomposition method has dense cracks on the surface and large crack width, and the electrolyte easily penetrates into the Ti substrate through the large cracks to corrode and dissolve the base material, and causes the peeling of the surface coating. On the other hand, non-conductive TiO is also formed2The thin layer also has an influence on the activity of the electrode, and the activity is inevitably reduced in the long-term use process, namely, the catalytic activity is ineffective.
In order to solve the above problems, the chinese patent office disclosed an invention patent application of a method for preparing a titanium electrode with a titanium dioxide nanotube-ruthenium titanium oxide coating on 2.27.2018, with application publication number CN107740138A, which includes: pretreatment of a titanium substrate; placing a pretreated titanium sheet serving as an anode and a large-area platinum mesh serving as a cathode in an electrolyte solution, then applying direct-current constant voltage to the two electrodes for anodic oxidation, keeping the temperature of the electrolyte solution constant and stirring the electrolyte solution in the anodic oxidation process, taking out the oxidized titanium sheet, namely the TiO nanotube/Ti electrode after the anodic oxidation is finished, ultrasonically cleaning the titanium sheet by using ethanol and water, annealing the titanium sheet, and cooling the titanium sheet to room temperature for later use; and coating the coating liquid on the surface of the TiO nanotube/Ti electrode by adopting a brush coating method, and drying, thermally oxidizing and cooling to obtain the TiO nanotube/Ti electrode. In the technical scheme, however, the anodic oxidation process is considered firstly, stirring is carried out in the process of preparing the titanium oxide nanotube array by anodic oxidation, the stirring can improve the uniformity of the electrolyte, however, the growth orientation of the titanium oxide nanotube array is lowered, the lowering of the growth orientation of the titanium oxide nanotube array causes problems such as uneven channels formed and poor surface flatness, and even partial cell clogging, the prepared coating liquid is also not suitable for direct coating, the coating uniformity of the coating liquid with the components is poor due to the problems of fluidity and the like during coating, and in addition, the evenness of the surface of the titanium oxide nanotube array is poor, the uniformity of the ruthenium-titanium oxide coating formed by coating is extremely poor, so that the electrochemical performance of the ruthenium-titanium oxide coating is reduced, the service life of an electrode is influenced and the like.
Disclosure of Invention
The invention provides a ruthenium-tantalum chlorine evolution electrode, a preparation method and a test method thereof, aiming at solving the problems that the existing ruthenium-tantalum chlorine evolution electrode has large-width and compact cracks, a titanium matrix is easy to corrode and peel off the surface layer due to electrolyte leakage in the using process, an insulated titanium oxide film is formed between the titanium matrix and a ruthenium-tantalum coating on the surface layer under the corrosion action of the electrolyte, the peeling off of the surface layer is further aggravated, the activity of the whole electrode is greatly reduced, the catalytic activity is lost and the like. It mainly realizes the following purpose: the bonding strength of a titanium substrate and the surface ruthenium-tantalum oxide is improved, and the stability of the surface ruthenium-tantalum oxide is improved; preparing an ordered and compact titanium oxide nanorod array structure, and forming a channel through the titanium oxide nanorod array structure; thirdly, a smooth charge transfer path with a large specific surface area is formed through the similar channel, so that the catalytic activity of the electrode is further improved; fourthly, the uniformity and the bonding strength of the ruthenium-tantalum oxide bonding layer on the surface layer are improved, and the electrocatalytic activity is improved; and fifthly, improving an electrode testing system, and deducing the service life of the electrode under the daily use condition through an empirical formula.
In order to achieve the purpose, the invention adopts the following technical scheme.
A ruthenium-tantalum chlorine-evolution electrode is provided,
the ruthenium-tantalum chlorine evolution electrode substrate is titanium, and a ruthenium-tantalum mixture covers the surface of the substrate;
the ruthenium-tantalum mixture is ruthenium oxide and tantalum oxide;
and a TNTs intermediate layer is grown between the substrate and the RuTa mixture.
The titanium matrix and the RuTa mixture layer are common chlorine evolution electrode combined structures, but in the invention, a highly ordered and compact TNTs (ordered titanium dioxide nanotube array structure) intermediate layer grows between the RuTa mixture and the titanium matrix, two ends of a nanorod of the TNTs intermediate layer are respectively connected with the titanium matrix and the RuTa mixture (RuTa oxide), the connection is stable and the strength is high, compared with the combination and contact with a flat surface, the RuTa mixture and the intermediate layer with the array structure can obviously generate higher combination strength, and because of the high ordering of the TNTs intermediate layer, a gap formed between the nanorod and the nanorod can be regarded as a channel-like structure when the TNTs intermediate layer is used for charge transmission, compared with a disordered nanorod array, the channel-like structure formed by the ordered array is more uniform, compact and smoother, so that the charge transfer is more efficient, the integral electrode has higher catalytic activity and longer service life.
A method for preparing a ruthenium-tantalum chlorine evolution electrode,
the method comprises the following steps:
1) taking metal titanium as a titanium matrix, pretreating the titanium matrix, taking the titanium matrix as an anode, building an electrochemical system to carry out anodic oxidation on the titanium matrix, and drying and carrying out heat treatment on the titanium matrix after the anodic oxidation to obtain a precursor;
2) dispersing ruthenium oxide in water to form ruthenium dispersion liquid, preparing ethanol/isopropanol mixed liquid, adding tantalum pentachloride into the ethanol/isopropanol mixed liquid, uniformly dissolving to form tantalum solution, mixing the ruthenium dispersion liquid and the tantalum solution, and standing and aging to obtain precursor liquid;
3) and dispersing the precursor liquid on the surface of the precursor, and then, placing the precursor liquid under a vacuum condition or in a protective atmosphere for heat treatment to prepare the ruthenium-tantalum chlorine evolution electrode.
The method is simple and efficient, and compared with the existing preparation process, the method firstly prepares the highly-ordered and compact TNTs intermediate layer by controlling the anodic oxidation process, prepares the precursor liquid with different components from the conventional coating liquid for coating so as to improve the uniformity of the prepared ruthenium-tantalum oxide layer, selects the volatile ethanol/isopropanol as the main solvent part, can realize the rapid volatilization of gas in the drying and forming process, further reduces the defects of pores, cracks and the like generated by the gas in the whole ruthenium-tantalum oxide layer, improves the compactness of the ruthenium-tantalum oxide layer, and improves the catalytic activity and the service life of the electrode.
As a preference, the first and second liquid crystal compositions are,
step 1) the pretreatment process comprises:
and mechanically grinding the surface of the titanium substrate by using No. 1-5 abrasive paper until the surface is smooth and has no obvious scratch, then placing the titanium substrate in absolute ethyl alcohol for ultrasonic degreasing, then placing the titanium substrate in a polishing solution for polishing, and washing and drying the titanium substrate by using deionized water.
The method is a conventional pretreatment operation, and has strong applicability and simple operation.
As a preference, the first and second liquid crystal compositions are,
step 1) in the anodic oxidation electrochemical system:
the electrolyte is 0.5-3 wt% of hydrofluoric acid solution;
the cathode comprises a graphite electrode and a platinum electrode;
the oxidation voltage is 15-25V;
the oxidation time is 15-25 min;
step 1) in the heat treatment process:
the heat treatment temperature is 420-480 ℃;
the heat treatment time is 90-150 min.
In an electrochemical system, the concentration, the oxidation voltage and the oxidation time of partial hydrofluoric acid solution of the electrolyte are controlled, the thickness of the TNTs intermediate layer can be controlled, the thickness degree of the nano-rods, the compactness of the nano-rod array and the like can be realized, and a better TNTs intermediate layer structure can be obtained within the range of the conditions;
during the heat treatment, the bonding strength of the TNTs intermediate layer and the titanium matrix is mainly improved, and the structure of the TNTs intermediate layer can be improved to a certain extent.
As a preference, the first and second liquid crystal compositions are,
step 2) during the preparation of the ruthenium dispersion:
controlling the mass ratio of ruthenium oxide to water to be (0.9-1.1): (19-24);
step 2) during the preparation process of the tantalum solution:
the volume ratio of ethanol to isopropanol in the ethanol/isopropanol mixed solution is 1 (0.8-1.2);
controlling the volume ratio of the mass of the tantalum pentachloride to the ethanol/isopropanol mixed solution to be (1-2): (5-10);
step 2) in the precursor liquid preparation process:
the volume ratio of the ruthenium dispersion liquid to the tantalum solution is (2.8-3.2): (6.8-7.2);
the standing and aging time is 20-28 h.
In the proportion, the ruthenium dispersion liquid and the tantalum solution are relatively dilute solutions, the uniformity of the ruthenium dispersion liquid and the tantalum solution in the final precursor liquid is mainly ensured, and the use amount of the tantalum solution is controlled to be relatively large when the precursor liquid is prepared, namely, the follow-up heat treatment drying can be rapidly carried out, and the defect that gas is mixed in the ruthenium-tantalum oxide layer to form can be effectively avoided.
As a preference, the first and second liquid crystal compositions are,
step 3) during the heat treatment:
the heat treatment temperature is 420-500 ℃;
the heat treatment time is 55-65 min.
The ruthenium-tantalum oxide layer can be dried through heat treatment, the drying efficiency can be improved through high-temperature heat treatment, and gas can be rapidly exhausted.
As a preference, the first and second liquid crystal compositions are,
the mode of dispersing the precursor liquid on the surface of the precursor in the step 3) comprises the following steps:
spraying, brushing and magnetron sputtering;
step 3) the protective atmosphere comprises:
nitrogen atmosphere, inert gas atmosphere.
The most common dispersion method is a brush coating method, which has the advantages of high efficiency and low cost, and the problem of nonuniform Ru-Ta oxide layer which is caused by the dispersion method is solved by improving the formula of the precursor liquid, so that the uniformity of the precursor liquid can be ensured.
A test method of a ruthenium-tantalum chlorine evolution electrode,
the test method comprises the following steps:
preparing an acid electrolyte, taking the ruthenium-tantalum chlorine-separating electrode as a working electrode and the metal titanium as a counter electrode, controlling the temperature of the whole system, then electrifying and continuously detecting the voltage of the system, measuring the time taken by the voltage to rise to the end voltage, and predicting the service life of the ruthenium-tantalum chlorine-separating electrode through the time.
The testing method specifically comprises the steps of taking 1mol/L NaCl solution as electrolyte, adjusting the pH of the electrolyte to be 1-3, taking a titanium sheet as a counter electrode, controlling the temperature of an electrolytic cell to be 40 +/-2 ℃, and applying current with the density of 0.6A/cm-2The service life of the electrode is predicted by the electrolysis time when the voltage of the electrolytic cell is increased by 5V under the constant current electrolysis condition.
The invention has the beneficial effects that:
1) the ruthenium-tantalum chlorine evolution electrode has good stability, catalytic activity and service life, and particularly shows obvious improvement on the aspect of service life;
2) the preparation method is simple and efficient;
3) the testing method can predict the service life of the electrode more accurately.
Drawings
FIG. 1 is a SEM image of the surface layer of the TaTa chlorine-evolving electrode prepared in accordance with the present invention;
FIG. 2 is a SEM image of the ruthenium tantalum chloride-evolving electrode prepared according to the embodiment of the present invention;
FIG. 3 is a diagram illustrating the distribution of elements of the RuTa chlorine evolution electrode according to an embodiment of the present invention;
FIG. 4 is a polarization curve of the TaTa chlorine evolution electrode according to the present invention;
FIG. 5 is a cyclic voltammogram of the TaTa chlorine evolution electrode prepared in the example of the present invention;
FIG. 6 is a graph showing the accelerated lifetime test of the TaTa chlorine evolution electrode manufactured in accordance with the present invention.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and the attached drawing figures. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Example 1
A method for preparing a ruthenium-tantalum chlorine evolution electrode,
the method comprises the following steps:
1) taking a titanium plate with the thickness of 1mm and the purity of more than or equal to 99.5wt% as a titanium matrix, and pretreating the titanium matrix, wherein the pretreatment process comprises the following steps: mechanically grinding the surface of the titanium substrate by using No. 1-5 abrasive paper until the surface is smooth and has no obvious scratch, then placing the titanium substrate in absolute ethyl alcohol for ultrasonic degreasing, then placing the titanium substrate in polishing solution for polishing, and washing and drying the titanium substrate by using deionized water;
after pretreatment, the anode is used as an anode, and an electrochemical system is built, wherein in the electrochemical system:
the electrolyte is 1.0wt% hydrofluoric acid solution, the cathode is a graphite electrode, the oxidation voltage is 20V, and the oxidation time is 20 min;
then, carrying out anodic oxidation on the titanium substrate, drying the titanium substrate after the anodic oxidation, and carrying out heat treatment at 450 ℃ for 120min to obtain a precursor;
2) dispersing ruthenium oxide in water to form a ruthenium dispersion, wherein:
the volume ratio of the mass of the ruthenium oxide to the water is 1: 19;
preparing an ethanol/isopropanol mixed solution, adding tantalum pentachloride into the ethanol/isopropanol mixed solution, uniformly dissolving to form a tantalum solution, wherein in the tantalum solution:
the volume ratio of the ethanol to the isopropanol in the ethanol/isopropanol mixed solution is 1: 1;
controlling the volume ratio of the mass of the tantalum pentachloride to the ethanol/isopropanol mixed solution to be 1: 5;
mixing the ruthenium dispersion liquid and the tantalum solution in a volume ratio of 3: 7, and standing and aging for 24 hours to obtain a precursor liquid;
3) and brushing the precursor liquid on the surface of the precursor, and then carrying out heat treatment at 450 ℃ for 60min under a vacuum condition or in a protective atmosphere to obtain the ruthenium-tantalum chlorine evolution electrode.
The prepared ruthenium-tantalum chlorine evolution electrode is tested, and the test method comprises the following steps:
using 1mol/L NaCl solution as electrolyte, adjusting the pH of the electrolyte to 2, using a titanium sheet as a counter electrode, controlling the temperature of the electrolytic cell to be 40 +/-2 ℃, and applying current density to be 0.6A/cm-2The service life of the electrode is predicted by the electrolysis time when the voltage of the electrolytic cell is increased by 5V under the constant current electrolysis condition.
The test shows that the service life is more than or equal to 320h, the service life is good, and the accelerated life test chart is shown in figure 6.
Meanwhile, the ruthenium-tantalum chlorine evolution electrode prepared in the embodiment is selected to carry out polarization test and cyclic performance test in the test method system, the obtained polarization curve is shown in figure 4, the cyclic voltammetry curve is shown in figure 5, and the ruthenium-tantalum chlorine evolution electrode has good catalytic activity.
In addition, the ruthenium-tantalum chlorine evolution electrode prepared in the embodiment is further characterized by comprising a scanning electron microscope and element distribution, the scanning electron microscope is used for detecting the structure as shown in a surface SEM image of fig. 1 and a cross-section SEM image of fig. 2, the surface ruthenium-tantalum oxide layer has the advantages of compactness, uniformity and complete structure, the structure of the TNTs intermediate layer is highly ordered, and the element distribution is characterized as shown in fig. 3 and is uniformly distributed.
Example 2
A method for preparing a ruthenium-tantalum chlorine evolution electrode,
the method comprises the following steps:
1) taking a titanium plate with the thickness of 1mm and the purity of more than or equal to 99.5wt% as a titanium matrix, and pretreating the titanium matrix, wherein the pretreatment process comprises the following steps: mechanically grinding the surface of the titanium substrate by using No. 1-5 abrasive paper until the surface is smooth and has no obvious scratch, then placing the titanium substrate in absolute ethyl alcohol for ultrasonic degreasing, then placing the titanium substrate in polishing solution for polishing, and washing and drying the titanium substrate by using deionized water;
after pretreatment, the anode is used as an anode, and an electrochemical system is built, wherein in the electrochemical system:
the electrolyte is 0.5wt% hydrofluoric acid solution, the cathode is a platinum electrode, the oxidation voltage is 25V, and the oxidation time is 15 min;
then, carrying out anodic oxidation on the titanium substrate, drying the titanium substrate after the anodic oxidation, and carrying out heat treatment at 420 ℃ for 150min to obtain a precursor;
2) dispersing ruthenium oxide in water to form a ruthenium dispersion, wherein:
the mass to water volume ratio of ruthenium oxide was 0.9: 19.1;
preparing an ethanol/isopropanol mixed solution, adding tantalum pentachloride into the ethanol/isopropanol mixed solution, uniformly dissolving to form a tantalum solution, wherein in the tantalum solution:
the volume ratio of the ethanol to the isopropanol in the ethanol/isopropanol mixed solution is 1: 0.8;
controlling the volume ratio of the mass of the tantalum pentachloride to the ethanol/isopropanol mixed solution to be 1: 10;
mixing the ruthenium dispersion liquid and the tantalum solution in a volume ratio of 2.8: 7.2, standing and aging for 20 hours to obtain a precursor liquid;
3) and brushing the precursor liquid on the surface of the precursor, and then placing the precursor liquid in a vacuum condition or a protective atmosphere for heat treatment at 420 ℃ for 65min to prepare the ruthenium-tantalum chlorine evolution electrode.
The prepared ruthenium-tantalum chlorine evolution electrode is tested, and the test method comprises the following steps:
using 1mol/L NaCl solution as electrolyte, adjusting the pH of the electrolyte to 3, using a titanium sheet as a counter electrode, controlling the temperature of the electrolytic cell to be 40 +/-2 ℃, and applying current density to be 0.6A/cm-2The service life of the electrode is predicted by the electrolysis time when the voltage of the electrolytic cell is increased by 5V under the constant current electrolysis condition.
Tests show that the service life of the material is more than or equal to 320h, and the material has a good service life.
Example 3
A method for preparing a ruthenium-tantalum chlorine evolution electrode,
the method comprises the following steps:
1) taking a titanium plate with the thickness of 1mm and the purity of more than or equal to 99.5wt% as a titanium matrix, and pretreating the titanium matrix, wherein the pretreatment process comprises the following steps: mechanically grinding the surface of the titanium substrate by using No. 1-5 abrasive paper until the surface is smooth and has no obvious scratch, then placing the titanium substrate in absolute ethyl alcohol for ultrasonic degreasing, then placing the titanium substrate in polishing solution for polishing, and washing and drying the titanium substrate by using deionized water;
after pretreatment, the anode is used as an anode, and an electrochemical system is built, wherein in the electrochemical system:
the electrolyte is 3wt% hydrofluoric acid solution, the cathode is a graphite electrode and a platinum electrode, the oxidation voltage is 15V, and the oxidation time is 25 min;
then, carrying out anodic oxidation on the titanium matrix, drying the titanium matrix after the anodic oxidation, and carrying out heat treatment at 480 ℃ for 90min to obtain a precursor;
2) dispersing ruthenium oxide in water to form a ruthenium dispersion, wherein:
the volume ratio of the mass of ruthenium oxide to water is 1.1: 23.9;
preparing an ethanol/isopropanol mixed solution, adding tantalum pentachloride into the ethanol/isopropanol mixed solution, uniformly dissolving to form a tantalum solution, wherein in the tantalum solution:
the volume ratio of the ethanol to the isopropanol in the ethanol/isopropanol mixed solution is 1: 1.2;
controlling the volume ratio of the mass of the tantalum pentachloride to the ethanol/isopropanol mixed solution to be 2: 5;
mixing the ruthenium dispersion liquid and the tantalum solution in a volume ratio of 3.2: 6.8, and standing and aging for 28h to obtain a precursor liquid;
3) and brushing the precursor liquid on the surface of the precursor, and then placing the precursor liquid in a vacuum condition or a protective atmosphere for heat treatment at 500 ℃ for 55min to prepare the ruthenium-tantalum chlorine evolution electrode.
The prepared ruthenium-tantalum chlorine evolution electrode is tested, and the test method comprises the following steps:
at 1mol/L NaCl solutionAdjusting the pH value of the electrolyte to 1, using a titanium sheet as a counter electrode, controlling the temperature of the electrolytic cell to be 40 +/-2 ℃, and applying current density to be 0.6A/cm-2The service life of the electrode is predicted by the electrolysis time when the voltage of the electrolytic cell is increased by 5V under the constant current electrolysis condition.
Tests show that the service life of the material is more than or equal to 320h, and the material has a good service life.
Example 4
A method for preparing a ruthenium-tantalum chlorine evolution electrode,
the method comprises the following steps:
1) taking a titanium plate with the thickness of 1mm and the purity of more than or equal to 99.5wt% as a titanium matrix, and pretreating the titanium matrix, wherein the pretreatment process comprises the following steps: mechanically grinding the surface of the titanium substrate by using No. 1-5 abrasive paper until the surface is smooth and has no obvious scratch, then placing the titanium substrate in absolute ethyl alcohol for ultrasonic degreasing, then placing the titanium substrate in polishing solution for polishing, and washing and drying the titanium substrate by using deionized water;
after pretreatment, the anode is used as an anode, and an electrochemical system is built, wherein in the electrochemical system:
the electrolyte is 1.0wt% hydrofluoric acid solution, the cathode is a graphite electrode, the oxidation voltage is 20V, and the oxidation time is 20 min;
then, carrying out anodic oxidation on the titanium substrate, drying the titanium substrate after the anodic oxidation, and carrying out heat treatment at 450 ℃ for 120min to obtain a precursor;
2) dispersing ruthenium oxide in water to form a ruthenium dispersion, wherein:
the volume ratio of the mass of the ruthenium oxide to the water is 1: 24;
preparing an ethanol/isopropanol mixed solution, adding tantalum pentachloride into the ethanol/isopropanol mixed solution, uniformly dissolving to form a tantalum solution, wherein in the tantalum solution:
the volume ratio of the ethanol to the isopropanol in the ethanol/isopropanol mixed solution is 1: 1;
controlling the volume ratio of the mass of the tantalum pentachloride to the ethanol/isopropanol mixed solution to be 1: 5;
mixing the ruthenium dispersion liquid and the tantalum solution in a volume ratio of 3: 7, and standing and aging for 24 hours to obtain a precursor liquid;
3) and brushing the precursor liquid on the surface of the precursor, and then carrying out heat treatment at 450 ℃ for 60min under a vacuum condition or in a protective atmosphere to obtain the ruthenium-tantalum chlorine evolution electrode.
The prepared ruthenium-tantalum chlorine evolution electrode is tested, and the test method comprises the following steps:
using 1mol/L NaCl solution as electrolyte, adjusting the pH of the electrolyte to 1, using a titanium sheet as a counter electrode, controlling the temperature of the electrolytic cell to be 40 +/-2 ℃, and applying current density to be 0.6A/cm-2The service life of the electrode is predicted by the electrolysis time when the voltage of the electrolytic cell is increased by 5V under the constant current electrolysis condition.
Tests show that the service life of the material is more than or equal to 320h, and the material has a good service life.
Example 5
A method for preparing a ruthenium-tantalum chlorine evolution electrode,
the method comprises the following steps:
1) taking a titanium plate with the thickness of 1mm and the purity of more than or equal to 99.5wt% as a titanium matrix, and pretreating the titanium matrix, wherein the pretreatment process comprises the following steps: mechanically grinding the surface of the titanium substrate by using No. 1-5 abrasive paper until the surface is smooth and has no obvious scratch, then placing the titanium substrate in absolute ethyl alcohol for ultrasonic degreasing, then placing the titanium substrate in polishing solution for polishing, and washing and drying the titanium substrate by using deionized water;
after pretreatment, the anode is used as an anode, and an electrochemical system is built, wherein in the electrochemical system:
the electrolyte is 1.0wt% hydrofluoric acid solution, the cathode is a graphite electrode, the oxidation voltage is 20V, and the oxidation time is 25 min;
then, carrying out anodic oxidation on the titanium substrate, drying the titanium substrate after the anodic oxidation, and carrying out heat treatment at 450 ℃ for 120min to obtain a precursor;
2) dispersing ruthenium oxide in water to form a ruthenium dispersion, wherein:
the volume ratio of the mass of the ruthenium oxide to the water is 1: 19;
preparing an ethanol/isopropanol mixed solution, adding tantalum pentachloride into the ethanol/isopropanol mixed solution, uniformly dissolving to form a tantalum solution, wherein in the tantalum solution:
the volume ratio of the ethanol to the isopropanol in the ethanol/isopropanol mixed solution is 1: 1;
controlling the volume ratio of the mass of the tantalum pentachloride to the ethanol/isopropanol mixed solution to be 1: 9;
mixing the ruthenium dispersion liquid and the tantalum solution in a volume ratio of 3: 7, and standing and aging for 24 hours to obtain a precursor liquid;
3) and brushing the precursor liquid on the surface of the precursor, and then carrying out heat treatment at 450 ℃ for 60min under a vacuum condition or in a protective atmosphere to obtain the ruthenium-tantalum chlorine evolution electrode.
The prepared ruthenium-tantalum chlorine evolution electrode is tested, and the test method comprises the following steps:
using 1mol/L NaCl solution as electrolyte, adjusting the pH of the electrolyte to 1, using a titanium sheet as a counter electrode, controlling the temperature of the electrolytic cell to be 40 +/-2 ℃, and applying current density to be 0.6A/cm-2The service life of the electrode is predicted by the electrolysis time when the voltage of the electrolytic cell is increased by 5V under the constant current electrolysis condition.
Tests show that the service life of the material is more than or equal to 320h, and the material has a good service life.
Claims (7)
1. A ruthenium-tantalum chlorine evolution electrode is characterized in that,
the ruthenium-tantalum chlorine evolution electrode substrate is titanium, and a ruthenium-tantalum mixture covers the surface of the substrate;
the ruthenium-tantalum mixture is ruthenium oxide and tantalum oxide;
and a TNTs intermediate layer is grown between the substrate and the RuTa mixture.
2. A method for producing the ruthenium tantalum chlorine evolving electrode according to claim 1,
the method comprises the following steps:
1) taking metal titanium as a titanium matrix, pretreating the titanium matrix, taking the titanium matrix as an anode, building an electrochemical system to carry out anodic oxidation on the titanium matrix, and drying and carrying out heat treatment on the titanium matrix after the anodic oxidation to obtain a precursor;
2) dispersing ruthenium oxide in water to form ruthenium dispersion liquid, preparing ethanol/isopropanol mixed liquid, adding tantalum pentachloride into the ethanol/isopropanol mixed liquid, uniformly dissolving to form tantalum solution, mixing the ruthenium dispersion liquid and the tantalum solution, and standing and aging to obtain precursor liquid;
3) and dispersing the precursor liquid on the surface of the precursor, and then, placing the precursor liquid under a vacuum condition or in a protective atmosphere for heat treatment to prepare the ruthenium-tantalum chlorine evolution electrode.
3. The method for preparing the RuTa chlorine evolution electrode according to claim 2,
step 1) the pretreatment process comprises:
and mechanically grinding the surface of the titanium substrate by using No. 1-5 abrasive paper until the surface is smooth and has no obvious scratch, then placing the titanium substrate in absolute ethyl alcohol for ultrasonic degreasing, then placing the titanium substrate in a polishing solution for polishing, and washing and drying the titanium substrate by using deionized water.
4. The method for producing a RuTa chlorine evolving electrode according to claim 2 or 3,
step 1) in the anodic oxidation electrochemical system:
the electrolyte is 0.5-3 wt% of hydrofluoric acid solution;
the cathode comprises a graphite electrode and a platinum electrode;
the oxidation voltage is 15-25V;
the oxidation time is 15-25 min;
step 1) in the heat treatment process:
the heat treatment temperature is 420-480 ℃;
the heat treatment time is 90-150 min.
5. The method for preparing the RuTa chlorine evolution electrode according to claim 2,
step 3) during the heat treatment:
the heat treatment temperature is 420-500 ℃;
the heat treatment time is 55-65 min.
6. The method for producing a RuTa chlorine evolving electrode according to claim 2 or 5, wherein the first electrode is a ruthenium-tantalum-chlorine evolving electrode,
the mode of dispersing the precursor liquid on the surface of the precursor in the step 3) comprises the following steps:
spraying, brushing and magnetron sputtering;
step 3) the protective atmosphere comprises:
nitrogen atmosphere, inert gas atmosphere.
7. A method for testing the RuTa chlorine evolution electrode according to claim 1,
the test method comprises the following steps:
preparing an acid electrolyte, taking the ruthenium-tantalum chlorine-separating electrode as a working electrode and the metal titanium as a counter electrode, controlling the temperature of the whole system, then electrifying and continuously detecting the voltage of the system, measuring the time taken by the voltage to rise to the end voltage, and predicting the service life of the ruthenium-tantalum chlorine-separating electrode through the time.
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